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Documentos de Profesional
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ZHU Xian (朱宪)**, ZHU Chao (朱超), ZHAO Liang (赵亮) and CHENG Hongbin (程洪斌)
Department of Chemical Engineering, School of Environment and Chemical Engineering, Shanghai University,
Shanghai 201800, China
Abstract The hydrolysis technology and reaction kinetics for amino acids production from fish proteins in sub-
critical water reactor without catalysts were investigated in a reactor with volume of 400 ml under the conditions of
reaction temperature from 180-320ºC, pressure from 5-26 MPa, and time from 5-60 min. The quality and quantity
of amino acids in hydrolysate were determined by bioLiquid chromatography, and 17 kinds of amino acids were
obtained. For the important 8 amino acids, the experiments were conducted to examine the effects of reaction tem-
perature, pressure and time on amino acids yield. The optimum conditions for high yield are obtained from the ex-
perimental results. It is found that the nitrogen and carbon dioxide atmosphere should be used for leucine, isoleu-
cine and histidine production while the air atmosphere might be used for other amino acids. The reaction time of 30
min and the experimental temperature of 220ºC, 240ºC and 260ºC were adopted for reaction kinetic research. The
total yield of amino acids versus reaction time have been examined experimentally. According to these experimental
data and under the condition of water excess, the macroscopic reaction kinetic equation of fish proteins hydrolysis
was obtained with the hydrolysis reaction order of 1.615 and the rate constants being 0.0017,0.0045 and 0.0097 at
220ºC, 240ºC and 260ºC respectively. The activation energy is 145.1 kJ·mol-1.
Keywords biomass, subcritical water, hydrolysis, reaction kinetics, amino acids
(1) Fish meat: purchased from market. The fish proteins hydrolysis was carried at 108°C
Figure 2 Compare of amino acid chromatogram between standard and sample hydrolysate of fish proteins
a—arginine; b—lysine; c—alanine; d—threonine; e—glycine; f—valine; g—proline; h—serine; i—isoleucine; j—leucine;
k—methionine; l—histidine; m—phenylalanine; n—glutamic acid; o—aspartate; p—cystine; q—tyrosine; r—tryptophan
Figure 4 Effect of reaction time on amino acid yield in Figure 5 Effect of pressure on amino acid yield in hydro-
hydrolysate (5 MPa, 260°C) lysate (260°C, 30 min)
◄ tyrosine; ► arginine; ◆ alanine; cystine; ■ isoleucine; ◄ tyrosine; ► arginine; ◆ alanine; cystine; ■ isoleucine;
● leucine; ▲ histidine; ▼ phenylalanine ● leucine; ▲ histidine; ▼ phenylalanine
hydrolysate rises with increasing reaction time at first, tyrosine and phenylalanine may be in air.
then decreases a little, except cystine which is like It is found that amino acids could be produced in
independent with reaction time. air, nitrogen or carbon dioxide, and it is much cheaper
than other methods of hydrolysis for breaking down
biomass which require expensive argon gas. This im-
3.3 Reaction pressure provement can help in industrial conversion of bio-
mass into a useful resource.
Figure 5 shows that the effect of pressure on
yield of amino acids in hydrolysate is not very marked 4 HYDROLYSIS KINETICS
as compared with temperature and time.
Biomass hydrolysis kinetics in super
3.4 Contrast of different atmosphere results (sub)-critical water have been studied [10-12]. Hy-
drolysis kinetics of fish proteins in sub-critical water
Figure 6 shows that the effect of different reac- was researched in this article.
tion atmosphere on different amino acid yield in hy-
drolysate is different. No matter whatever atmosphere 4.1 Kinetics formula of fish proteins hydrolysis
is used, there is a given temperature for maximum
yield of amino acid in hydrolysate. Fig. 6 suggest that
leucine, histidine and isoleucine should be hydrolyzed It is very difficult to analyze the fish protein, but
in atmosphere of nitrogen or carbon dioxide, while very easy to determine the total yield of amino acids
d (1 − X ) / dt = − k (1 − X )a (4)
Integrating Eq. (4) leads to Eq. (5):
values under different temperature are in Table 2. The
X = 1 − [1 − k (1 − a)t ]
1/(1− a )
(5) relationship between lnk and −1/ RT is shown in Fig. 8.
Ea is 145.1 kJ·mol 1 and the pre-exponential factor is
-
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