Energy Sources, Part A, 29:529–535, 2007

Copyright © Taylor & Francis Group, LLC

ISSN: 1556-7036 print/1556-7230 online
DOI: 10.1080/009083190966342

Anaerobic Biochemical Treatment of Wastewater

Containing Highly Concentrated
Organic Cyanogen

G. YAN
J. WANG
S. GUO
State Key Laboratory of Heavy Oil Processing
China University of Petroleum
Beijing, China

Abstract The first and second stage of chilled wastewater in acrylic fibersitrile
process and wastewater in acrylic fibers process are biodegraded under anaerobic
conditions. Toxicity of acrylonitrile, acetonitrile, polymers, and cyanide in the waste-
waters to the production of methane has been studied. Results suggest that the first
and second stage chilled wastewaters from acrylonitrile process and wastewater from
acrylic fibers process cannot be biodegraded well. CODBD of the first and second
stage chilled wastewaters from acrylonitrile process is 36.3 and 45.8. CODBD of
the wastewater from acrylic fibers process is 53.0. Acetonitrile, acrylonitrile, poly-
mers, and cyanide are toxic to anaerobic bacteria in the highly concentrated organic
cyanogens containing wastewater, inhibiting the methane-producing activity. Half inhi-
bition concentration (50% IC) to anaerobic methane-producing activity is 1,300, 320,
85, and 50 mg/L for polymers, acetonitrile, acrylonitrile, and cyanide, respectively.
Acrylonitrile is a metabolizing and physiological toxin, acetonitrile and polymers a
metabolizing toxin, and cyanide a physiological and sterilizing toxin.

Keywords 50% inhibition concentration, anaerobic biodegradation ability, organic

cyanogens containing wastewater, type of toxin

1. Introduction
Treatment of wastewater containing organic cyanogen is encountered in a lot of industrial
processes, such as metallurgical, chemical, mining, and petroleum refining processes.
Highly concentrated organic cyanogens containing wastewater is toxic and will produce
a severe pollution when discharged to the environment. It is difficult to be treated because
of its complexity in pollutant constitutions (Hulshoff, 1994; Wang, 1991; Hong, 1990;
Zhang, 1994). Many processes have been used in the treatment of inorganic cyanogens
containing wastewater, such as evaporation, concentration, biochemical treatment (for
low concentration), oxidation by peroxides or ozone, ion exchange, and adsorption by
active carbon, but relatively fewer to the organic cyanogens containing wastewater. In
general, incineration is used to treat the highly concentrated organic cyanogens containing
wastewater, and the costs are too high. Anaerobic biochemical degradation is one of the

Address correspondence to Shaohui Guo, Faculty of Chemical Engineering, China University

of Petroleum, Fuxue Rd., Changping, Beijing, 102200, China. E-mail: shguo@cup.edu.cn

529
530 G. Yan et al.

prospective methods and is used to treat the highly concentrated organic cyanogens
containing wastewater from the anaerobic pool of Fushun Acrylic Fiber Chemical Plant
in Liaoning Province, China.

2. Experimental
Factors considered in this study include inoculation sludge, different wastewater, nutrient,
microelement and buffer solution, etc.
Inoculation sludge was obtained from the anaerobic pool of Fushun Acrylic Fibers
Chemical Plant, VFA (acetic acid:acrylic acid:butyric acid = 72:23:4), nutrient solution
and microelement were added for cultivation, and then concentrated the sludge to about
12 gVSS/L (volatile and suspended solid content per L). The concentrated sludge was
stored in the refrigerator under 5◦ C for further use. Nutrient and microelement were
prepared as described in the literature (Hong, 1990). 10% NaHCO3 was used as the
buffer solution.
The apparatus used in this study consists of a 750 mL reactor, a 1,000 mL gas
collection bottle, a volumetric cylinder, and pipers. The experiments were carried out in
a temperature constant box, as shown in Figure 1. 500 mL solution was added in the
reactor and the temperature was kept at 30◦ C.
Inoculation sludge was added into the reactor, and then wastewater was added, mother
liquid of nutrient and microelement, the extracted substance of yeast and NaHCO3 , etc.
The solution in the reactor was made up to 500 mL with distilled water. For the blank
test, distilled water was used instead of the wastewater. Nitrogen was purged into the
reactor for 3 min before test.

3. Results and Discussion

3.1. Anaerobic Biochemical Degradation

The anaerobic biodegradation degree refers to the wastewater’s chemical oxygen demand
that can be degraded by anaerobic microorganism (Hulshoff, 1994), namely biodegrad-

Figure 1. The experimental apparatus.

 Anaerobic Biochemical Treatment of Wastewater 531

Figure 2. Anaerobic biodegradation of organic cyanogens containing wastewater, saccharose, and

phenol solution: BD%—anaerobic biodegraded COD%; M%—COD contributed by methane.

able COD, defined as CODBD . In the unacidified wastewater, CODBD was converted to
volatile acid (mainly acetic acid, acrylic acid, and butyric acid, defined VFA), H2 and bac-
teria’s cells. CODBD may be utilized by methane bacteria excepting from those converted
to bacteria’s cells. The COD that may be utilized by methane bacteria is defined as acid-
ificable COD (CODacid ), and it will be finally converted to methane and VFA. Through
measuring the yield of methane and the amount of VFA, defined as CODCH4 and CODvfa ,
respectively, the CODacid can be worked out, namely CODacid equals to CODCH4 plus
CODvfa . The CODcells can be estimated through material balance or through the conver-
sion efficiency of cells in the acid ferment and the production of methane. Therefore,
CODBD equals to CODCH4 plus CODvfa and CODcells .
The amount of methane produced was measured during the test at set time inter-
vals. The test stopped when ferment ended up. COD and VFA were measured, and the
amount of methane was converted to the COD value (30◦ C, 1 atm, the volume of methane
produced from 1 g COD is 405 mL). Saccharose and phenol are used for comparison.
Saccharose is easy to be biodegraded in the anaerobic condition and phenol’s biodegra-
dation is similar in some extent to the biodegradation performance of general petroleum
chemical plant’s wastewater.
The first and second stage chilled wastewater in acrylonitrile production and waste-
water in acrylic fibers production were compared to the saccharose and phenol (Figure 2).
The CODBD of these three highly concentrated organic cyanogen containing wastewater
studied was low. The CODBD % values of the first and second stage chilled wastewater in
acrylonitrile production and wastewater in acrylic fibers production were 36.3, 45.8 and
53, respectively, and the CODBD % values of phenol was 78, while that of sucrose was
as high as 97 mg/L. In Figure 2, M is methane conversion rate (M = CODCH4 /COD).
Wastewater’s M% was 30 for the first stage wastewater, 33.7 for the second stage, 40.4
for acrylic fibers, 70 for phenol solution, and 83 for sucrose solution, respectively. These
results indicate that methane is the final important product in the anaerobic biochemical
treatment.

3.2. The Toxicity of the Pollutants in the Organic Cyanogen Effluent

3.2.1. Anaerobic Sludge’s Relative Methane-producing Activity. Anaerobic sludge’s rela-
tive methane-producing activity (measured as the total volatile, suspend and solids, VSS)
532 G. Yan et al.

reflected the ability that sludge wipes off COD and the methane producing potential. The
used sludge’s concentration and VFA (base material) concentration were 1.5 gVSS·L−1
and 4 gCOD·L−1 , respectively. The gas produced was recorded until 80% VFA had been
consumed. Then wastewater was added again to repeat the operation. According to the
testing record, the figure of the methane produced vs. the time of ferment was drawn.
The biggest relative methane-producing activity, ACT = 0.570 gCODCH4 /(gVSS·d), was
obtained.

3.2.2. The Toxicity of the Main Pollutants in the High Concentration Organic Cyanogen
Effluent. The organic cyanogen in the wastewater cannot well be biodegraded because the
toxic substances depress the anaerobic oxidation. The main toxic substances in this re-
search are acrylonitrile, acetonitrile, polymer, and cyanide. Through the toxicity reflected
by producing methane, 50%IC (half inhibition concentration) was determined for differ-
ent toxic substances. After the sludge contacted with toxic substances for a set time, the
toxic substances containing ferment solution was removed, and VFA cultivation solution
without toxic substances was added. The recovering of sludge’s methane-producing ac-
tivity may reveal the mechanism of toxic substances depressing the anaerobic oxidation.
The testing equipment and procedures are the same as for the anaerobic sludge’s activity.
Recording the testing results, the cumulated yield of methane produced was obtained (see
Figures 3–6 below). The range of highest activity and the average slope in this range can
be determined, and the methane-producing activity of the blank and non-blank test was
obtained. The rate of sludge’s methane-producing activity in the testing concentration
of toxic substances and in the blank test can be calculated. The relationship between
ACT(%) and the concentration of toxic substance is shown in Figure 4. From the figure,
corresponding 50%IC could be gained.

3.2.3. Acrylonitrile. From Figure 3, we can see that acrylonitrile was very toxic to the
anaerobic bacteria, 50%IC is 85 mg/L. When the test began, there was an obvious de-
tention in producing methane. When the concentration of acrylonitrile was 40 mg/L, the
detention time of producing methane was 3 days. While the concentration was 80 mg/L,
the detention time was 5 days. However, when the concentration exceeded 120 mg/L,
sludge’s methane-producing activity was almost completely inhibited. In the test recov-
ering activity anaerobic sludge, inhibition to the remained activity in the sludge is not

Figure 3. Cumulated methane yield in the test of acrylonitrile’s toxicity.

 Anaerobic Biochemical Treatment of Wastewater 533

Figure 4. Cumulated methane yield in the test of acetonitrile’s toxicity.

Figure 5. Cumulated methane yield in the test of polymers’ toxicity.

Figure 6. Cumulated methane yield in the test of cyanide toxicity.

534 G. Yan et al.

obvious when the concentration of acrylonitrile is low. And the activity of anaerobic
sludge was well recovered. Such results indicate that low concentration acrylonitrile was
metabolizing toxin to anaerobic bacteria. High concentration acrylonitrile (>120 mg/L)
inhibits the activity of anaerobic sludge in the beginning of recovering test, but after
4 days, sludge’s activity was recovered and the yield of methane obviously increased.
It showed that high concentration acrylonitrile was physiological toxin.

3.2.4. Acetonitrile. The testing result is shown in Figure 4. Acetonitrile’s toxicity was
comparatively low to anaerobic bacteria. In the beginning of the test, no obvious deten-
tion of producing methane had been observed in low concentration of acetonitrile. When
the concentration of acetonitrile was 800 mg/L, sludge’s activity of producing methane
was almost completely inhibited. 50%IC was 320 mg/L. In the recovering test, inhibi-
tion was not obvious to sludge’s remaining activity in low concentration of acetonitrile.
Anaerobic sludge’s activity was recovered, indicating that low concentration acetonitrile
was metabolizing toxin to anaerobic bacteria.

3.2.5. Polymers. Polymers are mainly composed of lower polymer of acrylonitrile and
the copolymerization of acrylonitrile with cyanide. It exists as colloid or dissolves in
water. The former is difficult to be decomposed by microorganism, and the latter was
difficult to be acidified and the products contain a lot of NH3 -N that inhibits anaerobic
oxidation. Under testing conditions, as to anaerobic sludge, detention of polymers to
producing methane was about 2–3 days (Figure 5), and their 50%IC was 1,300 mg/L. In
the recovering test, anaerobic sludge’s activity was gradually recovered, and no detention
had been observed, indicating that polymers were metabolizing toxins.

3.2.6. Cyanide. Experimental result of the cyanide’s toxicity is shown in Figure 6.

Among the organic cyanogen pollutants studied, cyanide’s toxicity is the strongest. It
is apparently toxic to the sludge’s methane-producing activity even in low concentration,
and its 50%IC is 4.5 mg/L. Detention of cyanide to the methane-producing activity is
also obvious, as long as about 4 days. In the activity-recovering test, when cyanide’s
concentration exceeded 25 mg/L, anaerobic sludge’s activity is not recovered, show-
ing that anaerobic bacteria’s cell could not be restored again. Such results suggest that
cyanide is physiological toxin in the lower concentration, sterilizing toxin in the higher
concentration.

4. Conclusion
Compared to the phenol (CODBD is 78), CODBD of the first and second stage chilled
wastewaters from acrylonitrile process is 36.3 and 45.8. CODBD of the wastewater from
acrylic fibers process is 53.0. Such results suggest that these wastewaters cannot be
biodegraded well. Acetonitrile, acrylonitrile, polymers, and cyanide are toxic to anaerobic
bacteria in the highly concentrated organic cyanogens containing wastewater, inhibiting
the methane-producing activity. 50%IC is 1,300, 320, 85, and 50 mg/L for polymers,
acetonitrile, acrylonitrile, and cyanide, respectively. Acrylonitrile in low concentration
plays as metabolizing toxin; there is no inhibition of anaerobic sludge’s activity in the
initial stage of activity recovering test. Acrylonitrile in high concentration plays as phys-
iological toxin, but methane-producing activity can be recovered in a short time period.
Acetonitrile and polymers are metabolizing toxin.
 Anaerobic Biochemical Treatment of Wastewater 535

Acetonitrile, acrylonitrile, polymers, and cyanide are the main components that in-
fluence the CODBD of highly concentrated organic cyanogens containing wastewater.
Biodegradation ability of such wastewater can be modified with decreasing the concen-
tration of these pollutants.

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Wang, K. 1991. Low Concentration Wastewater’s Anaerobic–Hydrolytic Technology of Treatment.
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