Journal of Cleaner Production 20 (2012) 137e144

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Journal of Cleaner Production

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A novel and cleaner technological process of extracting L-glutamic acid from

fermentation broth by two-stage crystallization
Jianhua Zhang a, *, Lei Tang a, Hongjian Zhang a, Yuling Yang b, Zhonggui Mao a
a
The Key Laboratory of Industrial Biotechnology, Ministry of Education, School of Biotechnology, Jiangnan University, Wuxi 214122, PR China
b
Shandong Linghua Monosodium Glutamate Co., Ltd, ShanDong, Jining 272073, PR China

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

Article history: The fermentative L-glutamic acid is one of the important bio-products in the world. In 2009, China
Received 24 March 2011 produced 1.6 Mt of GA occupying more than 70% of the entire production globally. However, the prob-
Received in revised form lems of high sulfuric acid/liquid ammonia consumption and severe pollution in GA production process
5 August 2011
strongly limit the sustainable development of the fermentative GA industry. In this study, a novel GA
Accepted 5 August 2011
Available online 12 August 2011
extraction technology, two-stage crystallization technology (TSC), was proposed and testified in pilot
scale aiming at reducing sulfuric acid/liquid ammonia consumption and wastewater pollution in GA
production process. The proposed TSC process could totally recover 95% GA: extracting about 83% of GA
Keywords:
L-glutamic acid
from fermentation broth in the first-stage with isoelectric crystallization technique, and recovering more
Isoelectric crystallization than 70% of remaining GA in isoelectric mother liquor in the second-stage with evaporative crystalli-
Ion exchange zation technique. With the proposed TSC process, consumption of sulfuric acid, liquid ammonia and
Evaporative crystallization other supplemental materials could be substantially reduced, while the amount of high concentrated
Wastewater wastewater decreased from 9.8 m3/t-GA to 1.6 m3/t-GA. Through further treatments of evaporation and
Cleaner production centrifugation, the ammonium sulfate in the mother liquor originated from the second-stage crystalli-
zation could be recovered. The mother liquor after ammonium sulfate recovery could be consecutively
concentrated into a substance in semi-molten state again, and then the substance can be manufactured
as organic-inorganic compound fertilizers after quick cooling and extrusion granulating. Comparing with
the existing process of isoelectric crystallization with ion exchange (IEIE), the TSC process has the
advantages of high quality of GA product, less sulfuric acid/liquid ammonia consumption and no
wastewater/emission gas disposals. Furthermore, the solid waste could be utilized as the value-added
fertilizer at the same time. In this way, the proposed TSC process greatly promotes the economic and
environmental effect of the GA production process.
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction biodegradable materials (poly L-glutamate), attributing the poten-

Leglutamic acid (GA) is one of the most important amino acid
products with a wide range of applications. In pharmaceutical
industry, GA or its salt-derivates can be used as nutrition elements
and participate in body metabolism. At the same time, GA can
improve the function of nervous centralize and cortical brain for
neurasthenia patients (Williams et al., 2005). In food industry, L-
glutamate monosodium salt, namely monosodium glutamate
(MSG) is an important freshness enhancer widely used in the fields
of cooking as well as food processing, playing a key for food flavor
regulation (Tiziana et al., 2007; Cairns et al., 2007). A recent study
showed that the fermentative GA could also be used to produce
* Corresponding author. Tel./fax: þ86 510 85918296.
E-mail address: jhzh882@163.com (J. Zhang).
tial characteristics of application diversity for GA industry (Richard
and Margaritis, 2003; Ashiuchi et al., 2003).
Currently, most of GA is produced fermentatively. For nearly
a decade, GA industry develops rapidly, and the GA production
amount in China reaches 1.60 Mt (equivalent to 2.02 Mt of MSG)
that is about 70% of the global production. More than 200,000 t of
MSG is exported every year. However, the huge demands in
consumption of sulfuric acid, liquid ammonia and other chemical
supplemental compounds deteriorate the economic benefits in GA
production. On the other hand, the GA extraction process also
produces a large amount of high concentrated wastewater that
seriously pollutes the surrounding environment (Xue et al., 2008;
Yang et al., 2005). Therefore, Chinese MSG production enterprises
and the government urgently need economic and effective new
technique to solve these problems. In the past twenty years,

0959-6526/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jclepro.2011.08.004
138 J. Zhang et al. / Journal of Cleaner Production 20 (2012) 137e144
extreme efforts have been made by GA enterprises and related
scientific research groups in order to solve the above mentioned
problems (Xue et al., 2008; Yang et al., 2005; Bai, 2001). However,
many practices have proved that the huge amount of high
concentrated wastewater produced in GA extraction process is
difficult to be handled with the traditional end-of-pipe treatment
method.
During the past half century, it has been recognized that end-of-
pipe treatment is not a good ways for environmental pollution
control and the relatively high cost is also not acceptable by many
enterprises (Lindsey, 2011). It has been proved that only adopting
cleaner production technique and controlling pollution at the very
beginning in the production process, the problems and the high
operation cost in environment pollution control could be some-
what relieved (Schnitzer and Ulgiati, 2007; Frijns and Vlient, 1999).
In 2008, The National Ministry of Environmental Protection (NMEP)
of China issued the industrial cleaner production standard of MSG
[HJ 444-2008], requesting a comprehensive and overall imple-
mentation of cleaner production in MSG industry in China. The
current GA production situation indicated that high raw-materials
consumption and high pollution in GA extraction process are the
dominating factors limiting the economics of GA production
process. Modification of GA extraction technology has become one
of the major issues in achieving the target of "energy-saving, raw-
material consumption and emission reduction". In the past three
years, a novel and cleaner GA extraction technique, called two-
stage crystallization technology (TSC), was proposed and tested in
pilot scale (20,000 t-GA/y), in Shandong Linghua Monosodium
Glutamate Co., Ltd., of China. With this technique, a very good
performance in the terms of minimizing of raw-materials
consumption, wastewater disposal, and fresh water usage has
been achieved.
This paper was focused on introducing and reporting the
concepts of the novel cleaner technological process and its
performance in achieving of minimization in both wastewater and
raw materials including usage of sulfuric acid and liquid ammonia.
2. The current extracting process of GA: the IEIE process
2.1. The working principle of the IEIE process
GA is a zwitterion and it will be crystallized from fermentation
broth at its isoelectric point (pI, 3.22) where its solubility is lowest.
This is called isoelectric crystallization. When pH is lower than 3.22,
GA is mainly positively charged (cationic), and could be absorbed
by cationic resin. While pH is higher than 3.22, GA is mainly
negatively charged (anionic) and could be eluted from cationic
resin. The GA absorption/elution process is called ion exchange.
The details of the isoelectric crystallization and ion exchange
(IEIE) process could be described as follows:
Isoelectric crystallizationðpH 3:2Þ :
2GA þ 2Hþ þ SO2  2
4 02GA Y þ SO4 ð1Þ
AcidificationðpH 1:5Þ : 2GA þ 2Hþ þ SO2 þ 2
4 02GA þ SO4 (2)
Resin absorptionðpH 1:5Þ : R  SO3 NH4 þ GAþ 0R  SO3 GA
þ NHþ
4 (3)
2NHþ 2
4 þ SO4 5ðNH4 Þ2 SO4 (4)
þ
ElutionðpH 9:0Þ : R  SO3 GA þ NHþ
4 0R  SO3 NH4 þ GA (5)
2.2. The flow of the IEIE process
The flowchart of IEIE process is shown in Fig. 1. Using sulfuric
acid to adjust pH of fermentation broth from 6.5 to 3.2, about 75%
(w/w) of GA is recovered from broth by this isoelectric crystalli-
zation process followed solid/liquid separation with centrifugation.
However, the GA concentration in isoelectric mother liquid still
remains at about 20e25 g L1 (Liu et al., 2008). To increase GA
recovery ratio, pH of isoelectric mother liquor is further reduced to
1.5 with sulfuric acid allowing GA to be adsorbed with cationic
exchange resins. The GA adsorbed by resin is then eluted using
diluted ammonia solution, the eluted liquor is returned to
isoelectric crystallization process for re-crystallization. In this ion
exchange process, about 80% (w/w) of GA could be recovered from
the isoelectric mother liquor and the total recovery reaches around
95%. This process has the advantage of higher GA recovery,
however, sulfuric acid and liquid ammonia are largely consumed in
this process, and wastewater production is also huge.
2.3. Characteristics of IEIE process and wastewater treatment
2.3.1. Characteristics of wastewater
In IEIE process, two kinds of wastewater are disposed. One is the
waste mother liquor (wastewater-1, in Fig. 1) with high wastes
concentrations that is originated from cationic resin adsorption.
The other is the wastewater with middle wastes concentrations
(wastewater-2, in Fig. 1) that is produced during resin washing and
regeneration. The main components and the characteristics of the
two kinds of wastewater are summarized in Table 1. Wastewater-1
contains a large amount of organic and inorganic substances. The
organic substances mainly originated from fermentation process,
including cells (corynebacterium), residual sugar and other metab-
olites. Ammonium sulfate, the major inorganic substance in the
wastewater, is the product of adding liquid ammonia and sulfuric
acid during ion exchange process. Therefore, wastewater-1 char-
acterized with high solids concentration, COD and ammonia
nitrogen, as well as low pH, etc. The concentrations of waste solid
and COD in wastewater-2 are relatively low, but the ions concen-
tration of ammonia and sulfate remained at high level. Generally,
more than 12 m3 wastewater-1 and more than 10 m3 wastewater-2
are produced for 1 t GA production.
2.3.2. Treatment of wastewater
The wastewater-2 is generally treated by sequencing batch
reactor (SBR) anoxic-aerobic activated sludge process after adjust-
ing pH over 7.0 with Na2CO3 and mixing with some domestic
sewage. With the treatment using SBR anoxic-aerobic, wastewater-
2 could reach the ‘grade II’ disposal standard for MSG industry
(GB8978-96) (Huang et al., 2001). However, wastewater-1 is diffi-
cult to deal with because of the existence of high concentrated
sulfate salt. In anaerobic wastewater treatment process, sulfate-
reducing bacteria deoxidize sulfate salt into H2S that is toxic to
the denitrifying microorganisms and other microorganisms when
H2S reaches high level. In addition, the consumption of organic
carbon sources for sulfate-reducing bacteria is also harmful to the
anti-nitrification process (Cohen, 2006). Therefore, the conven-
tional anaerobic - aerobic treatment technique is difficult to handle
this kind of wastewater.
Some researches have proved that wastewater-1 could be used
as the raw materials after dilution to cultivate Candida halophila or
Rhodotorula glutinis to produce single cell protein (SCP). During the
processes, the COD removal rate exceeds 85% accompanied with
the valuable SCP production, however the removal rates of
ammonia nitrogen and sulfate ion were nearly zero (Xue et al.,
2008; Yang et al., 2005; Zheng et al., 2005). On the other hand,
 J. Zhang et al. / Journal of Cleaner Production 20 (2012) 137e144 139

Fig. 1. Flow chart of isoelectric crystallization with ion exchange process. The values for every step are given for production of 1.0 t of purity GA, based on our statistical survey of
Linghua monosodium Co., Ltd, an MSG production plant in ShanDong Province, China. The concentration of GA in fermentation broth is 100 g L1 in average.

the dilution operation requires fresh water supplement so that the
wastewater load would further increase.
The wastewater-1 contains up to 130 g L1 soluble solids, mainly
ammonium sulfate, which could be used as compound fertilizer
after concentrating and drying treatments. The industrial produc-
tion process of compound fertilizer through slurry-spraying gran-
ulation is shown in Fig. 2. After implementing the four-effect
evaporation of wastewater-1, the soluble solids concentration
could exceed 50% (w/w). Then, using high-temperature flue gas
spraying granulation, dry solid materials in the wastewater-1 can
be transferred into compound fertilizer (Zang et al., 2005a,b)
However, the slurry-spraying granulation process solves the
water pollution problem at the expense of causing serious exhaust
emission pollution (Zang et al., 2005a,b). In drying process, about
25,000 m3 exhaust gas is produced for producing 1 t compound
fertilizer (Li, 2009). With this process, a large number of acidic
waste liquor was actually released into the surrounding atmo-
sphere in the form of "acid steam”. The "acid steam" eventually
returns to the ground in the form of "acid rain" causing another
type’s ecological problem. In addition, extremely high drying
temperature (>450  C) would induce the formation of other hazard
gases and odor smell, which would deteriorate atmosphere envi-
ronment and be very harmful for the health of residents living in
surrounding area.
12 m3, pH2-3 15 kg
3 kg
Wastewater-1 PAAS Liquid ammonia

Table 1
Main components and characteristics of two kinds of wastewater from IEIE process.
12 m3, pH2-3 pH > 4.5 9.4 m3
Flocculation and flotation Four-effect evaporator condensate
Components Wastewatere1 Wastewatere2
GAg/L 41 ＞0.1
Microbial cells g/L 12  2 ＞0.3 340 kg 2.6 m3, >450°C
Acidic steam
Residue sugar g/L 53 ＞0.1 Wet microbial cells Slurry spraying granulation
(NH4)2SO4 g/L 89  6 ＞2.8
Others g/L 32  3 ＞0.5
Total soluble solids g/L 130  11 ＞3.5
1360 kg
pH 2.0e3.0 4.5e6.0
Compound fertilizers
COD g/L 87,000 ＞3000
BOD g/L 43,000 ＞1300
TN g/L 38,000 ＞1000 Fig. 2. The flowchart of compound fertilizers production through slurry-spraying
TP g/L 100 ＞10 granulation. The value of wastewater-1 is originated from Fig. 1, and the value of
rest steps are based on our statistical survey of Linghua monosodium Co., Ltd.
140 J. Zhang et al. / Journal of Cleaner Production 20 (2012) 137e144

12.7 m3, pH 3.2

10.5 m3, pH 6.5 0.87 t (purity)
Continuous isoelectric centrifuge
Fermentation broth GA-1 crystals
crystallization

12.0 m3, pH 3.2 1 kg

Isoelectric supernantants PAAS

11.8 m3, pH 3.2 400 kg

Flocculation and filter Wet microbial cells
420 kg 2.2 m3, pH<1 2.0 m3
Sulfuric acid Acidification
9.8 m3, pH 3.2 6.6 m3
Four-effect evaporator

3.2 m3, pH 3.2

1.5 m3 9.0 m3
Evaporation and GA
condensate
crystallization

0.13 t (purity)
centrifuge
GA-2 crystals

10 kg 1.6 m3, pH 4.5

Liquid ammonia Mother liquor

Evaporation and
(NH4)2SO4 0.6 m3
crystallization

390 kg
centrifuge
(NH4)2SO4 crystals

0.8 m3 0.3 m3
evaporation

Cooling, extrusion 720 kg

granulation Compound fertilizers

Fig. 3. The flowchart of the TSC CP process. The values for different steps are given for production of 1.0 t of GA, based on the pilot scale test result.

3. The TSC process for GA extraction Here, a new GA extraction process called TSC CP, was proposed
and then implemented in practice based on the following objec-
3.1. The concepts of the TSC process tives or considerations.

Generally, cleaner production strategies aim at the optimization
of material and energy flows by process modification (change of
raw materials, changes in operational practise, technological
changes), internal and external recycling (Fresner et al., 2010). With
the existing IEIE process, the GA extraction process itself controls
the consumption amounts of sulfuric acid and liquid ammonia,
wastewater load, as well as the emission level. As a result, GA
extraction technology actually dominates both the entire MSG
manufacturing costs and environmental effect. Therefore, devel-
opment of an optimal or novel GA extraction process is pursued in
increasing both economic efficiency and environmental effect
(Klemes et al., 2010).
(1) Simultaneously reducing the consumption amount of sulfuric
acid and liquid ammonia, as well as wastewater disposal load
originated from the traditional ion exchange process;
(2) Developing a new compound fertilizer production process to
eliminate the severe emission from the traditional slurry-
spraying granulation process;
(3) Comprehensively utilizing by-products formed in GA production
such as microbial cells protein, ammonium sulfate and compound
fertilizer, etc. to raise the entire products values and diversity;
(4) Recycling evaporation condensation water obtained in GA
extraction for fermentation medium preparation to save the
fresh-water resource.
 J. Zhang et al. / Journal of Cleaner Production 20 (2012) 137e144
Fig. 4. The flowchart of CIC process with the function of fine-grain elimination 1.
Continuous isoelectric crystallization tank (pH 3.2), 2. Fine-grain dissolving tank
(2) Flocculation-filtering method: Conventional flocculation with
(pH > 5.0), 3. Pump, 4. Fermentation broth (pH > 6.5), 5. Sulfuric acid(or other acidic
liquid), 6. The isoelectric mother liquor with fine grain (pH 3.2), 7. Discharged slurry
(pH 3.2).
3.2. The cleaner production approach of GA production: the TSC
process
The details of the proposed TSC process are shown in Fig. 3. The
pilot scale test had been carried out in Linghua MSG Co. Ltd.,
Shandong, China, during the past several years, and the feasibility
and effect of this new process were testified. The size of GA
extraction tank and working volume were 76 m3 and 11e12 m3/
batch, respectively. In 2010, a new product line based on TSC CP
model/concept was set up to process 20,000 t GA/y in Linghua MSG
Co. Ltd., Shandong, China.
Compared with the traditional IEIE with slurry-spraying gran-
ulation processes, the new technology integrating with GA evapo-
rative crystallization and melting & extrusion granulation
techniques greatly improved the comprehensive performance by
modification of batch isoelectric crystallization and flocculation in
air-float processes.
(1) Continuous isoelectric crystallization process (CIC) of GA: In
existing batch isoelectric crystallization process, some part of
Fig. 5. The photograph of liquids after two kinds of flocculation method A. the method mentioned in literature (Mai, 2002), 40  C, PAAS 50 mg L1, B. our work, 80  C, PAAS
50 mg L1.
141
GA product is in the form of fine grain with the diameter
deviation ranging 10e30 mm. The fine powder but with
considerable large size distribution is difficult to be separated
leading a lower recovery rate (Liu et al., 2008). As shown in
Fig. 4, in the new CIC process, the isoelectric mother liquor (pH
3.2) containing fine powders is continuously withdrawn from
isoelectric crystallization tank and mixed with fermentation
broth (pH > 6.5). Maintaining pH of the mixture over 5.0, fine
grains would be easily dissolved because of the increased
solubility. Then the mixture is pumped to crystallization tank.
By effectively eliminating the excessive fine grains, the residual
GA concentration in the mother liquor could be reduced to
18e20 g L1 maintaining GA recovery in the CIC process over
83%, which greatly reduces the burden in the subsequent step
e the evaporative crystallization (EC) for GA process.
air-flotation technique is a kind of end-treatment for waste-
water treatment, but the recovery of bacteria is low (about 85%)
(Mai, 2002). Meantime, a large amount of steam must be
consumed in cells drying because the water content in cells
obtained through air-flotation is very high (about 90%). It
should be noted that the cells removal in TSC process is to
create suitable conditions for GA crystallization while recover
the mother liquor at maximum extent to raise GA extraction
yield in the evaporative crystallization process. Aiming at this,
mother liquid obtained at CIC process is heated to 80  C using
the residual heat from multi-effect evaporator and evaporative
crystallization process, then the flocculant polyacrylic acid
sodium (PAAS) is added to gather the dispersive bacteria and
metamorphic protein. Through combining thermal denatur-
ation with flocculation technology, the removal rate of bacte-
rium could reach over 99% with the aid of a subsequent
filtration. The effect of two kinds of flocculation method is
shown in Fig. 5. With help of the modified treatment, the
flocculent mass is very easy to filter. In the pilot scale test using
a 30 m2 plate-and-frame filter, the filtration flux could reach
a level of 260e280 L/(m2 $h) and the water content of filtration
cake was around 60e63%. The COD in mother liquid declined
more than 42% after efficient bacteria removal.
142 J. Zhang et al. / Journal of Cleaner Production 20 (2012) 137e144

(3) Evaporative crystallization (EC) for GA process: The clear Table 3

mother liquid after removal of bacterium is concentrated about The comparison of raw materials and energy consumptions (per ton-GA).

3-folds in a four-effect evaporator, and the concentrated solu- Extraction Sulfuric acid Liquid ammonia Resin PAAS Steam Water
tion could form saturated solution when GA concentration processes kg/teGA kg/teGA kg/teGA kg/teGA t/teGA t/teGA
reaching a level of 60 g L1. GA can be precipitated as crystalloid TSC 420 10 0 1 4.4 0
if adding the seed crystals in the saturated solution and IEIE 850 135 5.4 3 4.9 ＞10
Reduce 430 125 5.4 2 0.5 ＞10
continuing the evaporation. Totally the clear mother liquor was
concentrated 6-folds (3-folds with four-effect evaporation and
2-folds with evaporative crystallization) and more than 70% of
GA in clear mother liquor could be recovered as crystalloid. The replaced by the proposed melting & extrusion granulation
total GA recovery achieved in the two steps extraction process process, where the severe emission problem could be
(pilot scale test) could reach 95%. Compared with ion exchange completely eliminated.
technology, the EC process can save huge amount of sulfuric
acid and liquid ammonia, while reducing the wastewater 3.3. The comparison of recovery and quality performance of GA in
disposal and fresh water supplement. two different processes

The mother liquor contains a large number of impurities, puri-
fication of GA from such a broth while simultaneously satisfying
a standard of high purity and recovery rate, is difficult. GA-2 (in
Fig. 3) obtained in the secondary-stage (evaporative crystallization)
contains more impurities than GA-1 obtained in the first-stage
(isoelectric crystallization), therefore GA-2 could not be directly
used as raw material for MSG product. In order to improve the
purity of GA-2, GA-2 was mixed and then dissolved with part of
isoelectric liquor after removal of bacterium and sulfuric acid, and
this mixture could be severed for pH adjustment of fermentation
broth in the CIC process (similar to the middle fraction of the IEIE
process shown in Fig. 1). With this re-crystallization process, GA
with high purity could be harvested.
(4) Recovery of ammonium sulfate by evaporative crystallization:
In GA fermentation process, continuously feeding ammonia to
control pH (6.5e7.0) of the fermentation broth and to supply
nitrogen source for GA synthesis is a must. In GA purification
stage, addition of sulfuric acid during isoelectric crystallization
process caused a large amount of ammonium sulfate accu-
mulation in isoelectric mother liquor. The content of soluble
solids in the mother liquor is about 60% after GA-2 separation,
among which ammonium sulfate occupies more than 50%
(absolute ammonium sulfate concentration, 33%w/w). Further
concentrating the mother liquor after secondary-stage crys-
tallization will lead to ammonium sulfate precipitatation, to
produce valuable ammonium sulfate crystalloid, a by-product
of GA manufacturing process and a starting material for
making inorganic fertilizer.
(5) Melting & extrusion granulating process: In the mother liquor
after removal of ammonium sulfate, the soluble solid
concentration reaches around 72%. Continuing to evaporate
the liquor at boiling point of 150  C, the soluble solids
concentration could rise to a level up to 97%. Under this
condition, all of the residual ammonium sulfate would be
crystallized out as fine powder but the residual sugar are in
melting state, so that the concentrates are actually in
a creamy state. Cooling the concentrates down to 70e80  C
and then implementing extrusion granulation, the creamy
materials eventually become solid particles, a potentially
useful organic-inorganic compound fertilizer. In this way, the
conventional slurry-spraying granulation process could be
The GA recovery rate obtained by TSC process is 95% in pilot
scale, which is equal to the GA recovery rate by traditional IEIE
process. However, the GA crystallization quality obtained with TSC
process improved greatly, particularly sulfuric acid ion concentra-
tion largely reduced in particular (Table 2). The main reason for this
is that the consumption of sulfuric acid is dramatically reduced
during TSC process. Improvement of GA quality is beneficial for the
subsequent MSG process. With performance improvement in color
and SO24 in GA, the activated carbon consumption reduces from
15 kg/t-MSG to 5 kg/t-MSG, and the consumption of steam reduces
from 5.2 t/t-MSG to 3.0 t/t-MSG. Therefore, the trade price of GA
will increase about 300 RMB/t-MSG.
3.4. The comparison of raw materials and energy consumptions in
the two different processes
The comparison is summarized in Table 3. Using evaporative
crystallization technique in TSC process to replace ion exchange
method, the sulfuric acid and liquid ammonia consumptions
reduced 50.6% and 92.6%, respectively. Although evaporation is
considered as a high energy consuming process, the extremely low
wastewater volume in TSC process (as compared with that of IEIE
process) even offsets the energy consuming features of evapora-
tion, causing the entire energy consumption reduction at certain
extent. Furthermore, the thermal efficiency of evaporation is higher
than that of drying with high-temperature flue gas. As a result,
using melting & granulating process technique in TSC process could
bring steam consumption down about 10% as compared with that
in IEIE process.
3.5. Recycle of condensate water
After four steps of evaporation, the water of isoelectric mother
liquor in TSC process is completely converted into condensate
water. The quality analysis result of the condensate water is shown
in Table 4. Due to entrainment effect in the evaporation process,
COD and NH3-N residual in the condensate water were slightly
higher than the disposal standard that direct disposal is prohibited.
The condensate water can be discharged to the surroundings after
aeration treatment, but it is not desirable in the terms of opera-
tional economics and fresh water saving. Our previous study has
verified that the condensate water could be reused as water

Table 2
The comparison of GA quality of two kinds of process. Table 4
Quality analysis of the condensate water from TSC process.
Extraction process Purity(dry) % SO2-
4 % Light transmittance %
TSC 97.5  0.5 0.3  0.1 38e55 Item pH COD mg/L NH3-N mg/L Conductivity ms/mm
IEIE 95  0.5 0.7  0.1 18e30 Condensate water 4.5e6.0 600e1000 30e70 200e400
 J. Zhang et al. / Journal of Cleaner Production 20 (2012) 137e144 143

Table 5 Table 8
The comparison of by-products per ton-GA of two kinds of process. The main composition analysis of organic-inorganic compound fertilizers.
a
Extraction Bacterial cells Ammonium sulfate Compound fertilizers Items Assay Required
process kg/teGA kg/teGA kg/teGA Total nutrient（N.P.K） g/100 g 16 15
IEIC 340 0 1360 Moisture g/100 g 3.0 10
TSC 400 390 720 Organic matter g/100 g 25 20
D-value þ60 þ390 640 pH 5.5e6.0 5.5e8.0
chloridion g Cl/100 g b
N.D. 3
a
Required: national standard for organic-inorganic compound fertilizers issued
by General Administration of Quality Supervision, Inspection and Quarantine of the
Table 6
PRC in 2002. Code: GB18877-2002.
The comparison of the contents of eight main amino acids from different protein b
N.D.: not detected.
sources.

Amino acid Protein source

Microbial cells g/100 g Soya bean meal g/100 g 90%. Table 7 summarized the analysis result of the ammonium
Lysine 2.94  0.25 2.60
sulfate. According to the national standard GB535-1995, it can not
Methionine 0.90  0.10 0.58 be used directly as commercial product, but it could be used as
Valine 3.81  0.23 1.99 a starting material for organic-inorganic compound fertilizers as
Leucine 4.87  0.44 3.47 certain amount of residual sugars and amino acids are contained in
Isoleuine 2.74  0.32 1.85
it.
Threonine 2.72  0.27 1.81
Phenylalanine 2.65  0.10 2.34
Tryptophan 0.64  0.04 0.68 (3) Organic-inorganic compound fertilizer
The amino acid analysis data of soybean meal originate from 10th edition of "China
to feed database" issued by China feed database information center in 1999. The last solid waste, the waste mother liquor after ammonium
sulfate separation, namely organic-inorganic compound fertilizers
resource for fermentation or supplement of losses in water circu- (OICF), is obtained by evaporation, cooling and extrusion granula-
lating cooling system, it would further increase operation perfor- tion. The main components in OICF are organic/inorganic
mance of the entire process (Duan et al., 2002). substances such as sugars, amino acids, soluble proteins, ammo-
nium sulfate and inorganic salts. The analysis results shown in
Table 8 indicated that it meets the national standard GB18877-
3.6. Reuse of solid waste
2002.
Solid by-products originated from TSC process mainly consist of
microbial cells, ammonium sulfate and Organic-inorganic 4. Comparison of economical efficiency in the two different
compound fertilizer. The production yields are shown in Figs. 2 extraction processes
and 3. The comparison results of the by-products obtained in two
different extraction processes were summarized in Table 5. The main consumptions and products per ton-GA production in
two different extraction processes are listed in Table 3 and Table 5.
(1) Microbial cells According to the current trade price of raw materials and
by-products, the comparison of economic evaluation between the
The major ingredient of microbial cells is protein. The analysis IEIE and TSC processes is shown in Table 9.
showed that crude protein content in dried microbial cells (cory- The Table 9 shows that, with the TSC process, the profit mainly
nebacterium) was about 75% and the pure one was more than 56%. comes from reductive consumption of sulfuric acid, liquid
The analysis result of eight essential amino acids in the protein is ammonia, etc., while the loss originates from the reduction in
shown in Table 6. Comparing with soybean meal, it shows that the compound fertilizers production. Overall, the economic profit of GA
microbial cells is a kind of superior protein resources for the feed. At production adopting TSC process increased more than RMB 1300/t-
present, price of this dried microbial cells reaches 3200 RMB per GA compared with that of using IEIE process.
ton in China. As for the equipment investment, the TSC process needs to add
evaporative crystallizer for recovering GA and ammonium sulfate,
(2) Ammonium sulfate however the ion exchange column, resins and the equipment of

Ammonium sulfate obtained by evaporative crystallization and Table 9

centrifugation is a kind of granular crystals, and its purity is about Profit enhancement when operating with TSC process over IECI process.

Table 7 Price Economic benefit

The composition analysis of ammonium sulfate. (RMB yuan/t)/(EURa/t) (RMB yuan/teGA)/(EUR/t-GA)

a
Quality improvement e þ300/32.6
Items Assay Required Sulfuric acid 600/65.2 þ258/28.0
Total nitrogen g/100 g 19.2  0.4 20.5 Liquid ammonia 2800/304.3 þ350/38.0
Moisture g/100 g 2.5 1 Resin 10/1.1 þ54/5.9
b
Free H2SO4 g/100 g N.D. 0.03 Flocculants 10000/1087.0 þ20/2.2
c
Total sugar g/100 g 2.0  0.5 N.R. Steam 160/17.4 þ80/8.7
c
Total amino acid g/100 g 3.8  0.2 N.R. Water resource 1.0/0.1 ＞þ10/1.1
c
Organic matter g/100 g 1.6  0.2 N.R. Bacterial cells 1.2/0.1 þ72/7.8
a Ammonium sulfate 800/87.0 þ312/33.9
Required: national standard for ammonium sulfate issued by General Admin-
Compound fertilizer 500/54.3 320/34.8
istration of Quality Supervision, Inspection and Quarantine of the PRC in 1995. Code:
Charge of sewage 10/1.1 ＞þ200/21.7
GB535-1995.
b Total e ＞þ1336/145.2
N.D.: not detected.
c a
N.R.: not required. 1 EUR z 9.2 RMB yuan.
144 J. Zhang et al. / Journal of Cleaner Production 20 (2012) 137e144
treating exhaust during slurry-spraying granulation in IEIE process
could be eliminated. The equipment investment for the two
extraction processes is considered to be equivalent in price-wise.
Acknowledgements
The work was supported by the national 863 project (grant
No.2006AA020303). We thank the Bureau of Wuxi Environment
Protection and Shandong Linghua monosodium glutamate Co., Ltd,
for their help and support.
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