Journal of Environmental Chemical Engineering 10 (2022) 108868

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Journal of Environmental Chemical Engineering

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Application prospect of advanced oxidation technology in wet process

phosphoric acid production
Xinxin Liu a,b, Fenghui Wu a,b, Guangfei Qu a,b,*, Caiyue Jin a,b, Ye Liu a,b, Lingrui Kuang a,b,
Hailin Li a,b, Xiuping Chen a,b, Zuoliang Wang a,b, Yinhan Cheng a,b
a
Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming, Yunnan 650500, China
b
National Regional Engineering Research Center-NCW, Kunming, Yunnan 650500, China

A R T I C L E I N F O
A B S T R A C T

Editor: Dr Y Liu
Phosphoric acid is a world-wide strategic resource related to the country ’s livelihood, and the demand for
phosphoric acid is increasing. The efficient and sufficient extraction of phosphoric acid from medium and
Keywords:
low- grade phosphate rock has become one of the main research techniques. This paper summarizes the
Advanced oxidation technology
Phosphoric acid
conventional and unconventional phosphoric acid processing technologies, compares their advantages and
Phosphate rock disadvantages, analyzes their applicability to different phosphate rocks and phosphorus recovery, and
Catalysis describes the migration and transformation characteristics of pollutants in by-products. In order to improve
the phosphorus recovery and reduce the environmental pollution risk of by-products, the method of using
advanced oxidation technology to enhance the recovery of phosphorus from medium and low-grade
phosphate rock is proposed. The residual amount of pollutants and environmental pollution risks of by-
products under the conditions of advanced oxidation technology were analyzed, aiming to provide new
theoretical support for the upgrading and trans- formation of phosphoric acid production technology and
process in phosphorus chemical enterprises.

1. Introduction
additives and it can be used as an acidifying agent, yeast nutrient or
nutrient enhancer [17]. In the medical field, phosphoric acid can be
The development and utilization technology of phosphoric acid
used to prepare phosphorus containing drugs, such as sodium glycer-
marks the development level of a country’s chemical industry [1].
ophosphate [18]. In summary, phosphoric acid involves all aspects of
Phosphorus chemical industry is a strategic industry in the world,
social production and life and is one of the indispensable resources
involving military industry, national defense, agriculture, food, energy,
[19–21].
chemical technology and other fields. With the rapid development of
The traditional production process of phosphoric acid is shown in
social science and technology, the demand for phosphorus resources
Fig. 2, mainly using the wet or thermal method is adopted. The wet
increases gradually [2–4]. As shown in Fig. 1, most of the products in
method mainly uses strong acid to replace weak acid [22,23]. In the
real life are derived from phosphoric acid as a raw material [5]. Phos-
thermal method, the phosphorus in the phosphate rock is transformed
phoric acid is an important raw material for phosphate fertilizer (su-
into phosphorus vapor overflow by heating, and the phosphorus is
perphosphate [6], potassium dihydrogen phosphate [7], ammonium
burned in the air to generate phosphorus pentoxide, which is then made
phosphate, etc.) [8–11], and also for the production of feed nutrients
by hydration [24,25]. Industrial phosphoric acid dissolved in distilled
(calcium dihydrogen phosphate) [8]. In industry, phosphoric acid was
water is required to remove impurities such as arsenic and heavy
used to generate insoluble phosphate layer on metal surfaces to protect
metals [26]. The filtrate meets the food grade requirements and is
metals from corrosion [12,13]. Phosphoric acid mixed with nitric acid
concentrated to prepare the finished edible phosphoric acid [27].
as chemical polishing agent [14] to improve the surface finish of
Traditional phos- phorus chemical processing exists high grade
metals. In addition, phosphoric acid was used as a raw material for the
requirements of original phosphate rock, single product structure, low
production of washing products, pesticides [15] and flame retardants
value of by-products, environmental unfriendliness and other issues,
[16]. In terms of food processing, phosphoric acid is one of the
which restrict the sus- tainable development of phosphorus chemical
important food
industry [25,28]. The

* Corresponding author at: Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming, Yunnan 650500, China.
E-mail address: qgflab@sina.com (G. Qu).

https://doi.org/10.1016/j.jece.2022.108868
Received 26 July 2022; Received in revised form 11 September 2022; Accepted 24 October 2022
Available online 27 October 2022
2213-3437/© 2022 Elsevier Ltd. All rights reserved.
X. Liu et al. Journal of Environmental Chemical Engineering 10 (2022) 108868

Fig. 1. Phosphoric acid derivatives.

Fig. 2. Common phosphoric acid production methods.

development of new technologies suitable for low and medium-grade

ore [36]. The grade distribution of phosphate rock in China is shown in
phosphorus ore, low by-product yield and environmentally friendly
Fig. 3, with an average grade is only 16.85%, which is far lower than
has become an important means to promote the sustainable develop-
Morocco (33%) [37–39]. Previous studies have provided evidence that
ment of phosphorus chemical industry.
phosphorus use is associated with ecological degradation [40]. Mineral
Phosphate rock (PR) is the core raw material in the production of
resource production in China is likely to peak between 2035 and 2045,
phosphoric acid and a global strategic resource. About 95.5% of phos-
and domestic phosphate production growth rates would be expected to
phate rock is sedimentary [29], and other important types of phosphate
decline, which would particularly affect high-quality phosphate rock
deposits are metamorphic phosphate rock and magmatic apatite phos-
[41]. Faced with the lack of high-grade phosphate rock, the processing
phate rock, both of which are one-time mineral resources [30–33].
and utilization of medium and low-grade phosphate rock is one of the
Table 1 shows the world phosphate rock reserves and mining volume
main research directions to alleviate the phosphate crisis [42,43].
in recent years, it can be seen that the distribution and production of
In order to achieve near zero emission of pollutants generated in the
phosphate ore is extremely uneven [34]. According to the statistics of
processing of low and medium-grade phosphate rock, relevant uncon-
the U.S. Geological Survey, the global proven phosphate rock reserves in
ventional phosphoric acid clean processing technologies are gradually
2019 were 69.488 billion tons, of which 11 countries or regions such
developed, mainly including unconventional wet process and thermal
as Morocco and Western Sahara, China, Algeria, Syria, Brazil, Saudi
process. Unconventional wet methods use nitric acid, hydrochloric
Ara- bia, South Africa, Egypt, Australia, the United States and Jordan
acid [68], phosphoric acid [22], sulfuric acid and other single or multi
had phosphate rock reserves of more than 1 billion tons [35]. Whereas
acid to digest phosphate rock [69,70] as a way to achieve efficient
China has many poor ores and few rich ores, it is difficult to utilize
replacement of phosphoric acid. The unconventional thermal method is
phosphate
an upgrade of

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Table 1
acid production technologies, compares the advantages and disadvan-
World phosphate rock storage and phosphate rock mining in 2021.
tages of each, analyzes the adaptability in different grades of
Country/ Phosphate rock reserves Phosphate rock output in Ref.
phosphate rock, and illustrates the application prospects of advanced
Region (100 million tons) 2021 (10000 tons)
oxidation technology in the field of phosphoric acid processing
China 32 8500 [44] technology. This paper provides a new research idea for the processing
Morocco 500 3800 [8]
America 10 2200 [45,
of medium and low-grade phosphate rock, which is expected to
46] improve the phosphorus recovery, reduce production cost, and enhance
Russia 6 1400 [47] resource utilization ef- ficiency of by-products.
Jordan 10 920 [48]
Saudi Arabia 14 850 [49]
2. Conventional phosphoric acid production
Brazil 17 550 [50]
Egypt 13 500 [51]
Vietnam 0.3 470 [30] The main raw material of conventional phosphoric acid production
Peru 3.1 380 [52] is high-grade phosphate rock, and the processing methods include
Tunisia 1 320 [53]
thermal method and wet method [76]. As the mainstream of thermal
Israel 0.62 300 [54]
Australia 12 220 [55]
processing, the traditional yellow phosphorus electric furnace has now
South Africa 14 200 [56] achieved industrial application. The yellow phosphorus phosphoric
Senegal 0.5 220 [57] acid has an irreplaceable position in the electronics and pharmaceutical
India 0.46 140 [58] industries, but there are problems such as high energy consumption,
Kazakhstan 2.6 150 [59]
unreasonable thermal energy utilization, large amount of sludge
Algeria 22 120 [60]
Finland / 100 [61]
phosphorus, and unfriendly environment, which makes the
Togo 0.3 120 [62] breakthrough of this tech- nology difficult [48,77–79]. At present,
Uzbekistan / 90 [63] there are few researches at home and abroad on the clean production
Turkey / 60 [64] technology of yellow phosphorus, except that Yunnan phosphating
Mexico 0.3 53 [65]
group, Zhengzhou University and Kunming University of Science and
Other 18.7 100 [66]
Global 2694.88.6 22000 [67] Technology carry out the research on the separation of dust and
phosphorus from yellow phosphorus flue gas and the synergistic
Note: The data in the table are from the National Bureau of Statistics of
activation technology of medium and trace element minerals and
China, the U.S. Geological Survey, and literatures.
silicon calcium. At present, the production of phosphoric acid using
sulfuric acid is a more mature process, which produces about 95% of
the heating method and phosphate ore heating method based on con- phosphoric acid, but the high content of impurities in phosphoric acid
ventional thermal processing. The rotary furnace [71–73] replaced the and phosphogypsum restricts the development of phosphorus
traditional electric furnace [24], the phosphate rock was wrapped with chemicals industry [80–82]. China’s phosphate rock is mainly of me-
SiO2 and C as pellets, and rotated in such a way that the phosphate ore dium and low grade and if traditional thermal/wet production is used,
was fully heated to reduce phosphorus, releasing phosphorus in the not only is the processing cost high, but it is also not friendly to the
form of phosphorus steam, and then reducing the temperature to environment. Therefore, research on unconventional and clean treat-
collect phosphorus, which eventually realized the processing and fine ment technologies for medium and low-grade phosphate rock to reduce
treat- ment of phosphoric acid. However, the by-products treatment of solid waste emissions at source is an urgent need for the current
the unconventional wet thermal phosphoric acid process is still a main development of phosphorus chemical industry in China.
constraint of the technology.
Due to the gradual development transition from high-grade phos- 2.1. Conventional wet production
phate rock to medium and low-grade phosphate ore, the developed
phosphate rock grades are harder to adapted to the previous phosphoric Conventional wet process phosphoric acid technology can be divided
acid processing technology. Therefore, an unconventional wet and into dihydrate method, hemihydrate-dihydrate method [83,84], hemi-
thermal phosphoric acid processing technology has been proposed. hydrate method and dihydrate-hemihydrate method [85] according to
Although the recovery rate of phosphorus has been improved, the uti- solid product form. The main technical conditions and reactions are
lization of by-products is still a significant problem [74,75]. Based on shown in Fig. 4. Dihydrate sulfuric acid is highly adaptable to
the current development of phosphate rock processing technology, this phosphate rock and relatively easy to produce conditions, and more
paper summarizes the conventional and unconventional phosphoric than 90% of wet process phosphoric acid production uses dihydrate
legal process [86,87]. The main difference between hemihydrate
method and

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Fig. 3. Phosphate rock grade in China.

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X. Liu et al. Journal of Environmental Chemical Engineering 10 (2022) 108868

Fig. 4. Conventional wet production process.

dihydrate method is the change of reaction conditions, while the basic

reactions remain unchanged [88]. The conventional wet process Table 2
mainly involves the reaction of phosphate rock (Ca5 (PO4) 3F) with The advantages and disadvantages of conventional wet phosphoric acid
strong acid to release heat and generate fluorine-containing waste gas, production.
as shown in
reaction Eq. (1) [23,89]. Technological Advantages Disadvantages Application
process
Ca5(PO4)3F+5 H2SO4+5nH2O=3 H3PO4+5CaSO4⋅nH2O+HF+Q (1) The dihydrate Mature technology, Low phosphoric acid Widely used;
method (one- stable operation and concentration and 90% of the
Dihydrate reaction can be divided into two steps, mainly including step method) high operation rate; high energy world uses this
reaction Eqs. (2) and (3). [86,87] Suitable for medium consumption; Large traditional
grade phosphate phosphorus loss; process.
Ca5(PO4)3F+7 H3PO4=5Ca(H2PO4)2+HF (2) rock; Low operating Phosphogypsum has
temperature, less strong acidity and
5Ca(H2PO4)2+5 H2SO4+10 H2O=10 H3PO4+5CaSO4.2H2O (3) fouling and many impurities.
corrosion problems.
Depending on the impurities contained in the phosphate ore, other The High phosphoric Difficult operation; Less applied,
side reactions (4—6) may occur. hemihydrate- acid concentration, High requirements but gradually
dihydrate significantly saving for raw material increasing in
SiO2+6HF=H2SiF6+2H2O (4) method (two- energy; P2O5 quality; High recent year
step method) recovery rate up to requirements for
H2SiF6=2HF+SiF4 (5) [96] 98%; High quality materials and large
of phosphogypsum. investment in
2 H2SiF6+SiO2=2H2O+3SiF4 (6) equipment.
The hemihydrate Obtain 40% P2O5 Serious phosphorus Less
SiF4 enters the tail gas absorption system together with other method (one- finished phosphoric loss (90% P2O5); application
step method) acid; Short process Unstable
gaseous by-products generated during the reaction. The fluorine-
flow; Low production; Low
containing gas produces H2SiF6 on SiF4 and precipitates silica gel. The investment. operation rate; High
relevant reac- tion equations are (7—11) [23,90,91]. material
requirements.
SiF4+(n+2)H2O=2 H2SiF6+SiO2⋅nH2O (7) The dihydrate- Phosphoric acid Long process times Few operating
hemihydrate contains about 35% and high investment equipments in
Fe2O3+2H3PO4=2FePO4+3H2O (8) method (two- P2O5; 98% in equipment; High the world
step method) phosphorus material
Al2O3+2H3PO4=2AlPO4+3H2O (9) [85] recovery rate; requirements;
produce as a by- Complex
Na2O+H2SiF6=Na2SiF6+H2O (10) product α- High pretreatment.
utilization value of
K2O6+H2SiF6=K2SiF6+H2O (11) α-hemihydrate
gypsum and
There are other side reactions in phosphate rock due to the presence phosphogypsum.
of carbonate (12—14).

CaCO3+H2SO4=CaSO4+H2O+CO2 (12)
products. The main component of the solid by-product (phosphogyp-
CaCO3⋅MgCO3+H2SO4=CaSO4+MgSO4+2 H2O+2CO2 (13) sum) of the conventional wet process is calcium sulfate. The main
solid products of the dihydrate process are CaSO 4.2 H2O, CaSO4.0.5
MgCO3+2 H3PO4=Mg(H2PO4)2+CO2+H2O (14)
H2O (α-hemihydrate gypsum, β-hemihydrate gypsum) and CaSO 4,
Impurities such as Fe, Al, Mg and organic matter mixed in the ma- which belong to the saturated structure. The main solid product of the
terial will make the material thicken, poor liquidity, and reduce the hemi- hydrate process is CaSO4.0.5 H2O, the hemihydrate-dihydrate
quality of gypsum, and ultimately affect the resource utilization of by- method and the dihydrate-hemihydrate method mainly generate solid
by- products CaSO4.2 H2O and CaSO4.0.5 H2O in different order [22].
5
 X. Liu et al. Journal of Environmental Chemical Engineering 10 (2022) 108868

Fig. 5. Conventional thermal production.

development of phosphorus chemical industry, while the dihydrate-

Table 3
Comparison of advantages and disadvantages of different processes for con- hemihydrate method is still immature and mostly in the laboratory and
ventional thermal phosphoric acid production. pilot stage. Therefore, it is necessary to develop new technologies suit-
able for the processing of medium and low-grade phosphate rock and the
Conventional Advantages Disadvantages Application
utilization of its by-products.
thermal
production
Electric furnace
Simple process, High corrosion Global
2.2. Conventional thermal production
two-step
easy to control, resistance of adoption
process
high safety factor equipment, high risk The conventional thermal phosphoric acid production process
of production of environmental mainly includes one-step conversion process and two-step conversion
process. pollution, high
process, as shown in Fig. 5 [25]. One-step conversion is a process
construction cost.
One step blast where the combustion of phosphate rock and the hydration reaction of
Low safety factor, Not yet
furnace process
Relatively low strong corrosive industrialized phos- phorus pentoxide components occur simultaneously in the same
construction cost effect, needs t reac- tion vessel. The second step conversion process is phosphate ore
and simple process. manual cooling.
Oxygen enriched reduction to obtain sublimated phosphate powder, in which the phos-
High temperature Not yet
air phosphorus
High production requirements, large industrialized
phorus fraction is converted into liquid substances by dust removal and
oxide process condensation, and then the phosphoric acid product is prepared by
efficiency of amount of air
phosphoric acid, required and high combustion, hydration and mist removal process [24].
which can produce risk of Conventional thermal production processes mainly include electric
electronic grade environmental
furnace two-step process, one-step blast furnace process, oxygen
phosphoric acid. pollution.
Optimized
High catalyst cost Not yet
enriched air phosphorus oxidation process, optimized oxidation
oxidation
With catalyst, the and high industrialized process, and steam phosphorus process [97]. The advantages and
process and
steam
production temperature disadvantages of different processes are shown in Table 3. Among
efficiency of required.
phosphorus them, the electric furnace two-step method is widely used, and the
phosphoric acid is
process
high and the purity
other processes are still in the laboratory and pilot test stage [98].
can be controlled. Conventional thermal pro- duction process was mainly used to prepare
high purity phosphoric acid, it has high energy consumption, high
environmental pollution risk, high
The advantages and disadvantages of different conventional wet production cost, and is not suitable for medium and low-grade phos-
process phosphoric acid production processes are shown in Table 2. The phate rock. Therefore, traditional thermal production processes need to
crystallization mechanism of dihydrate [92] or hemihydrate gypsum be upgraded and improved and new technologies need to be developed.
involves new crystal (crystal nucleus) formation and crystal growth, and
they both depend on the solubility of gypsum in the reactant slurry. 3. Unconventional phosphoric acid production
Supersaturation not only determines the crystallization rate, but also
affects the size, shape and thickness of crystals, which in turn affects the In order to improve phosphorus yield and reduce the risk of envi-
properties of the generated gypsum [93]. Supersaturation is mainly ronmental pollution, the unconventional wet and thermal production
controlled by the content of free sulfate in the reaction slurry. The methods suitable for the processing of medium and low-grade
quality of filtration and washing is determined by the crystalline form of phosphate rocks are proposed.
calcium sulfate [94]. Factors affecting the particle size and shape of
calcium sulfate crystal include phosphate ore particle size, free sulfuric
3.1. Unconventional wet production
acid concentration, phosphoric acid concentration, solid content in
slurry, impurities, reaction temperature, reaction time, slurry return
Unconventional wet methods mainly include hydrochloric acid
volume, mixing strength, feeding speed, etc. Calcium sulfate has three
method, nitric acid method and phosphorus sulfur two-step method
different hydrated crystal forms (hemihydrate, anhydrous and dihydrate
[99], as shown in Fig. 6. The preparation of phosphoric acid by the
[95]) and the shape is influenced by the phosphorus pentoxide content.
hydrochloric acid method started in the 1960 s [100]. Israeli mining
Conventional wet phosphoric acid is most commonly used in the
engineering company, Taiyuan Chemical Research Institute of the
dihydrate process, and its main solid by-product is phosphogypsum
former Ministry of chemical industry and other institutions have
(CaSO4.2 H2O). The by-products (phosphogypsum) of the dihydrate
carried out relevant research. The by-product (calcium chloride) of the
method have become an important environmental factor limiting the
hydro- chloric acid method can be converted into chlorine-based
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X. Liu et al. Journal of Environmental Chemical Engineering 10 (2022) 108868
compound

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X. Liu et al. Journal of Environmental Chemical Engineering 10 (2022) 108868

Fig. 6. Unconventional wet production.

Table 4 Republic were further improved and industrialized [103,104].

Comparison of advantages and disadvantages of different processes for uncon- However, the nitrous acid freezing technology requires high quality
ventional wet process phosphoric acid production. phosphate ore, low calcium removal rate, high energy consumption,
and insufficient utilization of associated resources [105]. Phosphorus
sulfur two-step
Unconventional Advantages Disadvantages Application process is one of the unconventional wet production technologies pro-
wet production
posed in recent years for the processing of medium and low-grade
Nitric acid method No solid waste Affected by nitric It was first phosphate rock [22]. It has high efficiency for phosphate rock decom-
generation; Low acid prices; High developed by
position and high phosphorus recovery, but the risk of environmental
environmental energy AODA
pollution risk. consumption and company, pollution of solid by-products (phosphogypsum) is high and
long process; known as uncertainty still exists in some process parameters. Compared with
Less application AODA method. conventional wet process, the industrial application of unconventional
in the industrial wet process is burdensome and the road is long.
filed.
Hydrochloric acid Wide source of Complex process The Mining
method [68,106] hydrochloric acid; flow; Difficult Engineering
The comparison of advantages and disadvantages of different pro-
Low requirements recovery of by- Corporation of cesses for unconventional wet process phosphoric acid production is
for phosphate ore products Israel (IMI) shown in Table 4. Although it has good adaptability to medium and
grade; Good (calcium developed the low- grade phosphate rock and high phosphorus recovery rate, it has a
solubility of by- chloride). famous IMI
high risk of environmental pollution and the technical process needs to
product of method.
phosphate ore by be further improved. While promoting the development of phosphorus
hydrochloric acid chemistry, researchers should also focus on the environmental impact
and can recover of by-products.
rare earth
elements
associated with 3.2. Unconventional thermal production
phosphate rock.
Phosphoric acid - Different from the Lack of process There is no In order to further reduce power consumption, Western Chemical
sulfuric acid two traditional maturity; Many literature
"pollute first, treat indicating
Research Corporation of the United States used an oil-fired rotary kiln
step method [107] process
later" approach; parameters need industrial to produce thermal phosphoric acid (KPa) from the mixture of
The treatment to be justified. application. phosphate ore, coke, and silica. There were two completely different
process is green zones in the rotary kiln, the reduction zone in the bottom layer used
and sustainable.
carbon to reduce phosphorus in phosphate ore to sublimate phosphorus
vapor; the oxidation zone on the solid layer burned the
phosphorus vapor in
fertilizer, but long-term application leads to soil hardening and acidifi- Uhde method in West Germany and the Kaltenbach-SCHZ method in
cation, and fails to solve the problem of serious pollution and solid France and Czech
waste discharge. Using nitric acid to decompose phosphate ore, the
phosphoric acid recovery rate is greater than 95%, no phosphogypsum
is produced, and the nitrate produced can then be used an excellent
fertilizer. At the beginning of the last century, the former Soviet
Union conducted in-depth research on the reaction mechanism of this
technology [101]. In 1928, Norway (Odda Smeltverk AG) successfully
developed the freezing technology to produce nitrophosphate fertilizer.
After that, the NorskHydro method in Norway [102], the Hoechst
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X. Liu et al. Journal of Environmental Chemical Engineering 10 (2022) 108868
oxidation to phosphorus pentoxide; the hot furnace gas containing
P2O5 was sent to the absorption device for cooling and absorption to
form thermal phosphoric acid. Western chemical research company
has car- ried out several development studies in the rotary kiln. Some
research institutes in China have made a breakthrough in the follow-
up study of KPa method, but the industrial production needs further
efforts. Because it is a difficult problem to strictly separate the
oxidation and reduction areas in the kiln [72].
Kiln process phosphoric acid has the same process principle as
thermal process phosphoric acid, in which the phosphate rock is
heated to high temperature with the participation of silicon dioxide,
the phos- phorus in the phosphate rock is reduced to gaseous
phosphorus,

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Table 5
CO+1/2 O2→2CO2 (17)
Advantages, disadvantages and application fields of advanced oxidation tech-
nology [114,115].
P2O5+3 H2O→2 H3PO4 (18)
Advanced Advantages Disadvantages Application
oxidation Although the process principles of kiln phosphoric acid and thermal
technology phosphoric acid are the same, their production processes are signifi-
Fenton oxidation cantly different. In the thermal phosphoric acid method, the reduction
Simple operation; More secondary Sewage
process
Low investment reactions and lower treatment field of phosphate rock (Eq. 15) occurs in the electric furnace, and the heat
[116–118]
and low running reaction efficiency; consumption in the warming reduction reaction is provided by electric
cost. High dosage of
inputs, producing
energy; The oxidation of phosphorus (Eq. 16) occurs in the
more iron sludge; combustion hydration tower, and its oxidation heat is removed by a
Need for subsequent large amount of circulating phosphoric acid and cooling water.
treatment. However, the kiln method of phosphoric acid uses a special technology
Ozonation High catalytic A certain degree of Sewage
process [119– to make the reduction (Eq. 15) and oxidation reactions (Eqs. 16–17)
activity, clear toxicity and treatment and
121] mechanism of corrosiveness. High medicine
occur in the same equipment (rotary kiln, tunnel kiln, etc.). In addition,
action, easy to equipment the heat generated by the reaction (16)-(17) is used to raise and lower
study and master; requirements. the tem- perature of the raw material in reaction (15), thus greatly
Solid catalyst, easy reducing the energy consumption for the phosphoric acid production.
to separate from
Compared with traditional thermal and wet phosphoric acid, kiln
water; Less
secondary process phosphoric acid can make full use of the low-grade siliceous
pollution and phosphate rock. Additionally, the phosphorus and fluorine in pellets
simple treatment exist in a stable mineral state and are not be dissolved by rainwater,
process.
Ultrasonic
making them more environmentally friendly.
Easy access to Consuming large Sewage
oxidation equipment and amounts of energy; treatment,
[122–125] simple operation; Stays in the medicine and 4. Application prospect of advanced oxidation technology in
Toxic organic laboratory stage. chemical phosphoric acid production
substances are industry
easily degraded
into small
The research process found that phosphorus recovery has become a
molecules with key consideration in the process replacement upgrade of phosphate
low or even no rock processing. However, phosphorus recovery is incomplete
toxicity; No (recovery rate 95%~98% and resource utilization of by-products is
secondary
difficult. Although the yield and environmental risk of by-products in
pollution will be
caused. the unconventional wet thermal production process is lower than that
Photocatalytic Mild reaction Difficulty in Sewage of conventional wet thermal, there is still a phase of resource
oxidation conditions; High recycling treatment, utilization to be explored. Advanced oxidation technology seems be
[126,127] oxidation photocatalyst catalytic promising for improving phosphorus recovery from low-grade
capacity; High materials; Harsh use purification and
reaction
phosphate rock and reducing environmental risk [108,109].
conditions. other fields
efficiency. Advanced oxidation technologies mainly include Fenton oxidation,
Wet air Wide range of Reaction equipment Sewage ozone oxidation, ultrasonic oxidation, photocatalytic oxidation, wet air
oxidation application; Good needs to be treatment, oxidation, and supercritical fluid oxidation. The related technical ad-
[128–130] treatment effect; resistant to high catalytic vantages, disadvantages and application fields are shown in Table 5. The
Less secondary temperatures, purification
pollution. pressures and
advanced oxidation process can produce hydroxyl radical (⋅OH) with
corrosion; strong oxidation ability, which can oxidize large organic compounds
Large investment that are difficult to degrade into small molecules with low or no
costs. toxicity under high temperature, high pressure, electricity, sound and
Supercritical High efficiency Harsh operating Sewage
fluid oxidation and complete
light conditions [108,110–112]. The researchers used microwave-
conditions; High treatment,
[131–133] treatment; Wide requirements for valuable
enhanced advanced oxidation process (MW-AOP) to effectively
application range; equipment and element release nutrients from the sludge [113]. When microwave radiation
No secondary instruments. extraction and was combined with hydrogen peroxide, the hydrogen peroxide could
pollution. other fields attack the organic fraction of sewage sludge, releasing nutrients (N, P),
proteins and amino acids. The phosphate particles in middle and low-
grade phosphate rock
phosphorus escapes and is oxidized to P2O5, and finally hydrated to in the digestion process are wrapped in organic matter and result in
produce phosphoric acid. The involved reactions are shown in Eqs. (15)- low phosphorus recovery, and the solid by-products produced cause a
(18). Due to the unsolved P2O5 reverse absorption degradation huge risk of environmental pollution. To a certain extent, the advanced
problem, the phosphorus yield was less than 60%, the kiln method oxidation technology can make up for the shortcomings of
phosphoric acid failed to be further industrialized. Since the 1980 s, conventional wet and thermal production processes.
Changsha Research Institute of mining and metallurgy has studied the
pilot scale technology of rotary kiln phosphoric acid and conducted the 4.1. Fenton oxidation process
semi- industrial trial of 10,000 tons of rotary kiln phosphoric acid
(85% H3PO4) in Baokang, Hubei Province. However, the problem of Based on the conventional wet process phosphoric acid production,
scale development needs to be solved urgently, and no large-scale Fenton oxidation was used to strengthen phosphorus recovery and
production unit has been built in China [71]. improve the efficiency of by-product utilization. The related action
Ca10(PO4)6F2+15 C+9SiO2→3/2 P4+15CO+9CaO⋅SiO2+CaF2 (15) mechanism is shown in Fig. 7 [108,116]. In the presence of acidic, Fe2+
conditions, Fenton oxidation can generate hydroxyl radical ( .OH) with
P4+5 O2→2 P2O5 (16) strong oxidation ability, which trigger more active oxygen species,
10
X. Liu et al. Journal of Environmental Chemical Engineering 10 (2022) 108868
thus degrading organic matter and macromolecular minerals in
phosphate

11
X. Liu et al.
Fig. 7. Fenton oxidation reaction mechanism.
rock [134]. The oxidation process is a chain reaction, where the pro-
duction of ⋅OH is the beginning of the chain, other reactive oxygen
species and reaction intermediates are the nodes of the chain, and the
reaction chain is not terminated until each reactive oxygen species is
consumed [135,136]. The reaction mechanism is complex, and the
reactive oxygen species mineralizes organic molecules and macromol-
ecules into CO2, H2O, oxidized minerals, etc. Benefiting from the
oxidation of organic matter and macromolecular minerals in the phos-
phate rock, the strong acid was in full contact with the phosphate rock
powder, which improved the phosphorus recovery. At the same time,
the reduction in the content of organic matter and complex mineral
components in solid by-products facilitates its resource utilization
[116, 137].
Li et al. proposed a green and clean method based on Fenton
oxidation theory to reduce the production of foam. The results showed
that the combined use of hydrogen peroxide and ferrous sulfate could
reduce foam formation; Fenton oxidation process was superior to the
traditional defoamer in reducing foam generation. By adjusting the so-
lution pH to make the organic substrate on the surface of phosphate
concentrate completely decomposed, soluble carbonate minerals are
easily dissolved and generation of carbon dioxide gas is inhibited. This
work study provides guidance for the use of advanced oxidation for foam
reduction in wet phosphoric acid process. More importantly, it
provides a theoretical basis for optimizing such processing methods
[116]. Liu’s
[108] team systematically studied the recovery rate of phosphorus
from phosphate rock and the residual amounts of hazardous
components in solid by-products under Fenton oxidation conditions.
Under the optimal reaction conditions of 0.04 mL/mL H2O2, 70 ◦C,
120 min, and 150 µm
12
Journal of Environmental Chemical Engineering 10 (2022) 108868
particle size, the leaching rate of O3-H2O2 reaction (OHR) could reach
88.4%, and the total organic carbon content in the leachate was
12.2 mg/L, which was significantly decreased by 79.9%. The experi-
mental results illustrate the advantages of oxidation technology in
strengthening the efficient leaching of phosphorus with low environ-
mental risk [138]. Du et al. [134] found that the microbubbles
produced by Fenton oxidation reaction have high oxidation activity,
which can greatly improve the decomposition efficiency of phosphate
rock. In summary, Fenton oxidation technology can decompose
phosphate rock efficiently, increase phosphorus recovery, improve by-
products quality, and reduce environmental risks, which has broad
application prospects.
4.2. Ozonation process
Ozone catalytic oxidation technology is an advanced oxidation
technology based on ozone. Using the strong oxidation and catalytic
properties of ozone could effectively solve the problem of incomplete
decomposition of phosphate rock, and the relevant principles are
shown in Fig. 8 [121,139,140]. There are two main oxidation modes
between O3 and phosphate rock, direct oxidation and indirect
oxidation. Direct oxidation is a direct oxidation reaction between O3
and macromolecular substances in phosphate rock (mainly including
organic matter and macromolecular minerals), which enhances the
effect of strong acid on phosphate rock and thus improves the
phosphorus replacement effi- ciency. Indirect oxidation is the
decomposition of O3 by some technical means to generate hydroxyl
radicals, which then react with phosphate rock in an oxidation reaction
[141]. In the direct oxidation process, O3 molecules react selectively
with phosphate rock components, and the
X. Liu et al. Journal of Environmental Chemical Engineering 10 (2022) 108868
Fig. 8. Ozone action mechanism.

13
X. Liu et al. Journal of Environmental Chemical Engineering 10 (2022) 108868

Fig. 9. Ultrasonic action mechanism.

decomposition of phosphate rock after oxidation is incomplete, mainly

decomposition of phosphate rock [144]. The reaction of strong acid
converting large-molecule phosphate minerals into small molecular
decomposing of phosphate rock is a flow solid non-catalytic reaction.
substances. These substances broken into small molecules is usually high
Under the "thermal effect" and "non-thermal effect" of ultrasound, the
decomposable, increasing the contact area between strong acid and
rate of phosphate rock decomposition by strong acid is influenced by
phosphate rock, thus improving the replacement efficiency of strong
ultrasonic power, reaction temperature, reaction time, and other
acid [142].
factors. With higher ultrasonic power, the ultrasonic density and solute
On the basis of wet process phosphoric acid, using ozone catalytic
molec- ular motion velocity increase, the impact flow from cavitation
oxidation technology to enhance phosphate rock digestion to produce
is strengthened, and the erosion of solid by-products increases [145].
phosphoric acid has a broad research prospect. In the conventional wet
Ultrasonic catalytic oxidation technology has the potential to be
production process, phosphate rock micro-particles are wrapped by
applied in the production of phosphoric acid by strong acid digestion
organic matter preventing the further decomposition of phosphate
of phosphate rock, which is expected to realize the full recycling and
rock. Ozone catalytic oxidation can not only destroy the organic
resource utilization of phosphorus resources. However, ultrasonic cat-
components in the phosphate rock, but also greatly reduce the organic
alytic oxidation technology has not been studied much in the solid-
components in the solid by-products, thus also improving the physical
liquid reaction of phosphate rock and strong acid. In this experiment,
properties (whiteness, etc.) of by-products, and helping to improve the
only the relationship between the acidification rate of phosphate rock
utilization efficiency of by-products.
and the ultrasonic power under isothermal conditions was investigated.
The kinetic study of ultrasonic liquid-solid reaction under non-
4.3. Ultrasonic oxidation isothermal condition has not been involved, which is also the direc-
tion of our future research. In foreign countries, ultrasonic chemistry
and chemical engineering has become a hot spot of research and has
The reaction principle of ultrasonic catalytic oxidation technology
made rapid development [146,147]; while in China, there are some
is mainly based on the phenomenon of acoustic cavitation. Ultrasonic
gaps in this field of research. Additionally, due to the complexity of
waves form cavitation bubbles at the bubbles in strong acid solution or
cavitation effect, the current research is often limited to the physical
on the surface of phosphate rock. The cavitation bubble fragmentation
perspective and lacks a complete and unified theory, and the ultrasonic
causes local high temperature (5000 K), high pressure (100 MPa) and
catalytic oxidation technology is in a period of continuous
acoustic luminescence, which promotes the generation of strong
improvement. How to apply ultrasonic technology to practical
oxidizing monomers such as hydroxyl radicals, as shown in Fig. 9
production reasonably and economically is an important problem for
[123, 143]. The highly oxidizing monomer digests the organic matter
us to think about in the future.
and macromolecular substances on the surface of phosphate rock
which in- creases the contact area between phosphate rock particles
and strong acid, and thus improves the phosphorus replacement 4.4. Photocatalytic oxidation
efficiency. Local high temperature and high pressure can improve the
phosphate rock digestion efficiency and achieve the high-efficiency
Light energy is a renewable green energy. Photocatalytic oxidation
leaching of phos- phorus. In addition, high temperature and high
enhanced phosphate rock dissolution technology improves the phos-
pressure change the original crystal morphology of solid by-products,
phorus recovery efficiency under the action of light on the basis of
which increases their utilization efficiency. In the process of phosphate
photocatalyst [148]. Photocatalysis oxidation technology requires
rock decomposition, the solidification film formed by calcium sulfate
photocatalysts or phosphate molecules to absorb electromagnetic radi-
crystals on the surface of the particles hinders the decomposition of
ation with specific wavelength to generate excited state molecules,
phosphate rock, and ul- trasonic intervention can improve the problem.
which then undergo chemical reactions to generate new substances or
Cavitation can continuously clean up the impurity layer on the sur-
intermediates, which in turn produce strong oxidizing radicals. Free
face of the calcium sulfate crystal and accelerate crystal growth. In
radicals oxidize organic components and macromolecular substances
addition, the turbulence, jet, shock wave and other effects make the
in phosphate rock to realize phosphorus release and efficient recovery,
boundary layer to form a cavitation cavity and reduce the thickness of
as shown in Fig. 10 [149–152].
the boundary layer and cause local turbulence in the bottom layer,
The efficient phosphorus release technology by photocatalytic
which help to eliminate the solidification film and accelerate the
enhanced phosphorus elimination has become one of the research fo-
cuses in the field of phosphoric acid production from phosphate rock.
14
X. Liu et al. Journal of Environmental Chemical Engineering 10 (2022) 108868

Fig. 10. Photocatalysis mechanism.

Fig. 11. Wet oxidation mechanism.

The application of photocatalytic oxidation technology in phosphoric

4.5. Wet air oxidation
acid production will greatly reduce phosphoric acid production costs
and promote the rapid development of phosphorus chemicals.
Wet catalytic oxidation technology uses oxygen-rich bodies or oxy-
Although photocatalytic oxidation technology is theoretically
gen as oxidant at high temperature (200–280 ℃) and high pressure (2–
promising, so far there is no relevant literature indicating its specific
8 MPa). This process accelerates the respiration reaction between
application in the field of phosphorus chemical industry. In order to
phosphate rock and oxidant to oxidize organic matter and macromo-
improve the recovery of phosphorus from low-grade phosphorus rock,
lecular minerals into CO2, N2, SO2, H2O and oxidized substances, thus
the research on the application of photocatalytic oxidation technology
fully replacing phosphorus. The relevant mechanisms are shown in
in phosphorus chemical industry cannot be ignored.
Fig. 11 [128,153–155].
The oxidant oxidizes the macromolecular substances in phosphate
rock increasing the contact area between phosphoric acid and
phosphate

Fig. 12. Supercritical fluid catalytic oxidation mechanism.

10
X. Liu et al. Journal of Environmental Chemical Engineering 10 (2022) 108868

electrocatalytic oxidation technology in the field of phosphorus

Fig. 13. Electrocatalysis mechanism.

rock, and improving the phosphorus replacement efficiency. At the same

time, the organic components in the solid by-products are fully
oxidized and harmful substances such as heavy metals are fully
leached, which greatly reduces the environmental pollution risk of
solid by-products and promotes the clean processing of phosphorus
resources. There is no relevant literature indicating that the wet
catalytic oxidation tech- nology can enhance the decomposition of
phosphate rock. In order to make up for the defects of the traditional
phosphoric acid production process, this technology has broad research
prospects.

4.6. Supercritical fluid oxidation

Supercritical fluid oxidation technology is a technology that

enables the deep oxidation of organic wastes or macromolecular
minerals in phosphate rock [131,156]. Supercritical fluids completely
oxidize organic matter or macromolecular minerals into clean H2O,
CO2, N2 and oxidized substances [157]. In supercritical system,
strong acid is co-soluble with phosphate rock. With the presence of
supercritical and strong acids, the production of phosphoric acid
increases, the organic components of phosphate rock are oxidized by
supercritical catalysis [158], while toxic and harmful components such
as heavy metals enter the liquid phase are collected. The method has
low risk of environmental pollution, high phosphorus recovery, and
high resource utilization value of the obtained solid by-products, but
the utilization cost needs to be considered. The specific action
mechanism is shown in Fig. 12 [133]. Supercritical fluid catalytic
oxidation technology has high research significance and value, but it
requires high equipment and process performance. Therefore, further
research is needed for the promotion and application of supercritical
fluid catalytic oxidation technology.

4.7. Electrocatalytic oxidation technology

Electrocatalytic oxidation technology is one of advanced oxidation

[159]. Compared with direct ozone oxidation, the electrocatalytic
oxidation system produces hydroxyl radical (⋅OH) with 105 times
higher reaction rates, and can react with almost all organic substances
or macromolecular minerals in phosphate rock. The effect of advanced
oxidation is stable and does not change with the residual organic sub-
stances in phosphate rock. The use of this technology can greatly
improve the decomposition efficiency of phosphate rock, shorten the
reaction time, greatly reduce the processing cost of phosphorus re-
sources, and promote the clean utilization of by-products [45,160]. Fig
13.
Electrocatalytic oxidation technology has potential application in
facilitating phosphate rock decomposition. However, few studies on
11
X. Liu et al. Journal of Environmental Chemical Engineering 10 (2022) 108868
resources have been reported. According to the mechanism analysis
of phosphoric acid preparation from phosphate rock, this technology
can enhance the whole reaction and greatly reduce the environmental
pollution risk of by-products, which is an environmentally friendly
phosphorus resource processing technology.

5. Conclusion and prospect

Phosphorus resource is a worldwide strategic resource. The tradi-

tional phosphorus resource utilization process is mostly applied to
high- grade phosphate rock with low phosphorus recovery rate,
accompanied by the risk of by-product and environmental pollution.
In addition, the residual phosphorus components in the by-products
pose a serious pollution threat to the ecological environment, which is
not conducive to the resource utilization of by-products. Due to the
increasing demand for phosphorus resources and decreasing
phosphate rock grade in the word, the traditional production process
of phosphorus resources has failed to meet the actual development
needs, therefore, the unconven- tional processing technology of
phosphorus resources has been pro- posed. The application of
unconventional technology in preparing phosphoric acid from
phosphate rock is still at the laboratory or pilot stage, moreover, the
process parameters, clean treatment of by-products and other issues
seriously hinder the development of this technology.
Advanced oxidation technology was put forward earlier, it has
been few studied in promoting phosphate rock decomposition.
Advanced oxidation technology has a broad research prospect in
enhancing phosphoric acid preparation from phosphate rock. In this
paper, the enhanced mechanisms of different advanced oxidation
techniques (Fenton oxidation, ozone oxidation, ultrasonic oxidation,
photocatalytic oxidation, supercritical fluid oxidation, etc.) in
preparing phosphoric acid from phosphate rock are discussed, aiming
to provide practical technical support for the development of
phosphorus chemical industry.

Declaration of Competing Interest

The authors declare that they have no known competing financial

interests or personal relationships that could have appeared to
influence the work reported in this paper.

Data Availability

The data that has been used is confidential.

Acknowledgements

Financial support for this project was provided by The National

Key Research and Development Plan-Ecological Link Technology for
Clean processing of Typical by-products of Unconventional
Wet/thermal Production (2018YFC1900203) and The National Key
Research and Development Plan- The environmental functional
materials of long- acting solidification/stabilizer for heavy metal
tailings pollution, tech- nologies and equipment etc
(2018YFC1801702), which is greatly acknowledged.

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