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Optimization of the removal of lignin and silica from rice husks with alkaline peroxide
Alireza Bazargan, Zhixuan Wang, John P. Barford, Junaid Saleem, Gordon McKay
PII: S0959-6526(20)30895-7
DOI: https://doi.org/10.1016/j.jclepro.2020.120848
Reference: JCLP 120848
Please cite this article as: Bazargan A, Wang Z, Barford JP, Saleem J, McKay G, Optimization of the
removal of lignin and silica from rice husks with alkaline peroxide, Journal of Cleaner Production (2020),
doi: https://doi.org/10.1016/j.jclepro.2020.120848.
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3 Alireza Bazargan a*, Zhixuan Wang b (equal contribution as the first author), John P. Barford c, Junaid
a
6 School of Environment, College of Engineering, University of Tehran, Iran.
b
7 Department of Chemical Engineering, Imperial College London, South Kensington Campus,
8 London, UK.
c
9 Department of Chemical and Biomolecular Engineering, Hong Kong University of Science and
d
11 Division of Sustainable Development, College of Science and Engineering, Hamad Bin Khalifa
13
14 *Corresponding Author:
17
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18 ABSTRACT
19 Rice husks surround rice grains, and are known to provide them with a protective lignocellulosic
20 cover. This biomass has many potential uses, such as biofuel production. However, the high
21 concentrations of lignin and silica limit its use, for example they hinder fermentation reactions. In
22 this study, both the delignification and silica removal from husks using a combination of hydrogen
23 peroxide and sodium hydroxide has been investigated. Response surface methodology has been used
24 to find the optimum conditions for maximizing lignin and silica removal, and solid yield. Three
25 independent variables, namely, NaOH concentration, H2O2 concentration and reaction temperature
26 were studied by using Box-Behnken design. The first optimization focused on maximum removal of
27 impurity, and was found at 8% NaOH, 1% H2O2 and 20°C. Under such conditions, 71.78% lignin
28 removal, 88.47% silica removal and 50.89% solid yield were achieved. The second optimization
29 emphasized the reduction of chemical costs, and was found at 5.29% NaOH, 1% H2O2 and 20°C;
30 resulting in 59.85% lignin removal, 75.13% ash removal and 59.21% solid yield.
31
32 KEYWORDS: Rice hulls and chaffs; Delignification; Alkaline Peroxide; Box Behnken; Response
33 Surface Methodology;
34
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35 Abbreviations
42
43 Highlights
44 1. Alkaline peroxide was used to extract lignin and silica from rice hulls
45 2. The treatment temperature, NaOH concentration, and H2O2 concentration were varied
46 3. With RSM, the silica ash removal, lignin removal, and solid yield were optimized
47 4. Nearly 51% solid yield was retained, with about 71% lignin and 88% silica removal
48 5. Nearly 60% solid yield is possible, with about 60% lignin and 75% silica removal
49
50
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51 Graphical abstract
52
53
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54 1. Introduction
55 Biomass valorization, that is the conversion of biomass into valuable products such as chemicals and
56 biofuels, has gained widespread interest in recent years initiating a global research effort to find
57 alternatives to fossil fuels to achieve a more sustainable future. The hundreds of millions of tons of
58 lignocellulosic biomass produced each year could be the source for bioenergy as well as feedstock
59 for biorefineries rather than being discarded as biowaste or burned. The abundance of biomass, such
60 as rice husks, and their widespread geographical distribution are advantageous points which may
61 bring economic and environmental benefits if used properly (S. Ullah et al., 2019). Agricultural
62 residues, are both widespread and relatively cheap, making them a suitable feedstock for sugar
63 platform biorefining. Because of the depletion of traditional fuels and the consequent environmental
64 issues, biofuels are becoming widely accepted as one of the most suitable alternatives (Sharma et al.,
65 2019). Another important point is that the valorization of biowaste and lignocellulosic residues can
66 have the added bonus of relieving stress from exhausted raw natural resources.
67
68 In the case of the rice farming industry, well over 100 million tons of rice husks are generated every
69 year around the globe, most of which are abandoned as a waste material. The husk (also known as
70 the hull or chaff) is the outer layer, covering and protecting the rice grain (Azat et al., 2019). In
71 recent years, considerable research has been directed to investigate the alternative use of rice husks.
72 For example, Quispe et al. (2009) conducted a life cycle assessment study on using the husks for
73 heating, and concluded that although the environmental impacts (i.e., global warming, acidification,
74 and eutrophication categories) to obtain 1 MJ from rice husk are markedly less than obtaining 1 MJ
75 from coal, in water depletion, using coal has a much smaller impact (Quispe et al., 2019). In another
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76 study, the multigeneration of electricity, cooling, freshwater, hydrogen and ammonia from rice husks
77 has been proposed (Siddiqui et al., 2019). Research efforts attempting to find suitable applications
78 for rice husks are diverse, ranging from the extraction of chemicals using ultrasonic assisted ionic
79 liquids (Z. Ullah et al., 2019) to the synthesis of magnesium-silicate-hydrate cements (Sonat and
80 Unluer, 2019) and geopolymers (Wen et al., 2019). A recent review has focused on the many
81 applications of rice husks, in particular due to their pozzolanic content, mainly stemming from their
83
84 As far as the fermentation of biomass is concerned, cellulose is usually the main substrate. However,
85 in rice husks, the cellulosic cell wall, occurs as a complex matrix of lignocellulose bound by lignin
86 and hemicellulose (Mussatto and Teixeira, 2010). The polymeric compounds which comprise
87 cellulose are linked together by hydrogen bonding, forming a microfibril structure. The husk has a
88 crystalline structure making the material both insoluble and nondegradable. Since lignin and
89 cellulose crystallinity may prevent the accessibility of enzymes to the sugars, lignocellulosic
90 substrates are not suitable in their raw form for fermentation reactions (Mussatto and Teixeira, 2010).
91 Meanwhile, the ash content in rice husks is also considered as one of the major obstacles to their use
92 as biofuels (A. Bazargan et al., 2014). As the main component of ash in rice husk, silica can lead to
94
95 Currently, there are various companies which use biomass from rice paddies in fermentation
96 reactions for biofuel production. Some examples include projects in Eniwa City, Hokkaido, Japan
97 (by Taisei Corporation and Sapporo Breweries) and Katagami City, Akita Prefecture, Japan (by Akita
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98 Agriculture Public Corporation and Kawasaki Plant Systems Co.). But these projects have focused
99 on the fermentation of rice straw and have forgone using husks. This could be due to the higher
100 volume of rice straws and lower content of silica and lignin content as the latter, which makes them
101 suitable for fermentation process (Contreras et al., 2012). Meanwhile, although Power Gen Global
102 PLC (UK) owns patents (developed by Colusa Biomass Energy) for fermentation of both rice straws
103 and husks, the company has positioned itself to focus more on straws (rather than husks).
104
105 In the current study, to achieve the selective separation of cellulose from the lignocellulosic matrix,
106 the rice husks have been treated using alkaline peroxide pretreatment (AHP). Response Surface
107 Methodology (RSM) based on Box–Behnken Design (BBD) was applied for optimizing NaOH
108 concentration, H2O2 concentration, and temperature. The objective is to remove lignin and ash
109 (primarily composed of silica), while still retaining most cellulosic components in the solid residues
110 to facilitate subsequent fermentation reactions. RSM is a statistical method (Demir Delil et al., 2019),
111 which can be used to discern the relationship between a set of independent variables with one or
112 more response variables (Taqui et al., 2019). The ultimate goal of this study, is to render the husks
113 more suitable for utilization in biofuel production. The main limitation of the current study is the fact
114 that the rice husks are from a certain strain cultivated in Hunan China. Since there are dozens of
115 popular rice strains across the globe, each with a different composition of husks, the results obtained
116 herein may not be completely replicable for husks from other regions. Using lower temperatures,
117 atmospheric pressure, and modeling the process for a wide range of operating conditions are among
118 the main strengths and benefits of the current study. Although there are a number of sporadic studies
119 regarding AHP of lignocellulosic materials in recent years, a parametric research applying RSM has
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120 not been studied for both delignification performance and the extraction of silica from rice husks. For
121 instance, a previous study has used RSM to study the removal of lignin from vineyard pruning
122 residues by AHP treatment, but the silica content was unfortunately not considered as a response
124
125 2. Overview
126 An excellent review covering the various aspects of alkaline peroxide treatment of biomass has
127 recently shown that this is a promising method to make lignocellulosic biowastes more accessible for
128 fermentation reactions (Ho et al., 2019). For example, fermentable sugars produced from the
129 enzymatic conversion of alkaline peroxide oxidative pretreated sugarcane bagasse has shown
130 promise (Ayeni et al., 2019). Coconut biomass has also been investigated for improved fermentation
131 following alkaline and alkaline peroxide treatment showing improved performance in glucose
132 conversion and ethanol yield (Gonçalves et al., 2014). Elsewhere, rapeseed straw has been treated
133 with 5% (v/v) H2O2 at 50 °C for 1 h in order to improve ethanol production. Magnesium sulfate was
134 also added to the mix in order to improve ethanol production efficiency (Karagöz et al., 2012).
135
136 As far as rice husks are concerned, pretreatment with various acids and bases has shown an increase
137 in pore size and pore volume, which is expected to be beneficial in terms of accessibility for
138 microorganisms in the fermentation process (Ang et al., 2013). Alkaline peroxide treatment and
139 enzymatic saccharification were investigated for the conversion of cellulose and hemicellulose
140 within rice husks to simple sugars, achieving very high conversion to sugars (as high as 96%) by
141 saccharification of the liquid and solid fractions separately after 24 h treatment with 7.5% hydrogen
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142 peroxide at pH 11.5 and 35C (Saha and Cotta, 2007). Cabrera et al. (2014) studied the effects of
143 alkaline and alkaline peroxide treatment at 30°C and atmospheric pressure on rice hulls and straws to
144 obtain improved enzymatic hydrolysis. Interestingly, the researchers concluded that the best results
145 were not achieved when the highest biomass loss (lowest solid yield) occurred. The optimum
146 treatment conditions for that study were 4% alkaline peroxide treatment for 48 hours (Cabrera et al.,
147 2014).
148
149 Researchers have gone as far as using the harsh conditions of wet air oxidation combined with
150 peroxide treatment in order to inflict disruptions on lignocellulosic biomass (sawdust and rice husk)
151 in order to make the material more accessible for enzymatic hydrolysis (Ayeni et al., 2013; Banerjee
152 et al., 2011). Steam explosion alongside alkaline peroxide treatment has also been used (Chen et al.,
153 2008).
154
155 Overall, AHP treatment can promote a saponification reaction to break the intermolecular ester bond
156 linkages between the xylan hemicellulose and lignin (Asgher et al., 2013). The linkage break will
157 reduce the degree of crystallinity and polymerization thus breaking the crosslinkages existing in the
158 lignin. With hydrogen peroxide treatment, H2O2 can decompose into superoxide anions (·O2-) and
159 hydroxyl radicals (·OH) with heat, thus promoting the breakdown of the lignin structure. Since
160 chemicals are costly, lower concentrations of the AHP solution can make this process more
161 economical. After the AHP process, the lignocellulosic matrix becomes more fragile and open
163
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164 An advantage of using AHP for biomass valorization is the ability of this treatment to reduce the
165 production of some fermentation inhibitors such as furfural. In contrast with ultrasound pretreatment
166 which does not reduce acetic acid formation, AHP is capable of doing so, which proves useful in
167 hydrolysate detoxification (Li et al., 2016). It has also been shown that AHP has limited degradation
168 effects on cellulose and hemicellulose, which are wanted components in the later stages of
170 reactions (Correia et al., 2013). An operational advantage of AHP is that it is effective in relatively
171 mild conditions, namely atmospheric pressure and room temperature. Obviously, the mild conditions
172 lower capital costs and operational costs are due to the lower energy usage (Banerjee et al., 2012).
173 However, it should be noted that a higher temperature and pressure may help expediate the AHP
174 process. In addition, the need for alkaline conditions will result in corrosion, requiring suitable
175 reaction vessels, as well as a potential safety risk. The chemical costs, the need for neutralization of
176 alkaline after the treatment, and the long processing times have been identified as the major obstacles
178
179
182 Anhydrous sodium hydroxide pellets (Catalog No.: AC20606), and H2O2 (50 wt% solution, Catalog
183 No.: H341-500) were obtained from Fisher-Scientific (Waltham, MA). Rice husk samples were
184 provided by Peako Biomass Engineering Company Limited and originated from the Hunan region of
185 China. The rice husk samples were initially washed using deionized water at 50°C for 2 h and dried
186 in an oven overnight. The dried rice husk samples were then dewaxed using a mixture of
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187 toluene-ethanol (2:1, v/v) by Soxhlet extraction for 6 h because of the presence of alcohols, fatty
188 acids, and certain other extractives. The dewaxed samples were washed with water at 50 °C for 2 h
189 and returned to the oven to be dried overnight (Wong et al., 2003).
190
191 The constituents of the rice husks were determined by the methods of Han and Rowell (1997) who
192 defined plant materials as the sum of extractives, holocellulose, lignin, and inorganic ash. Neutral
193 solvents, water, toluene or ethanol, or a combination of solvents are employed to remove extractives
195
197 Concentrations of 2.0, 5.0, and 8.0% (w/v sodium hydroxide) and 1.0, 3.0 and 5.0% (w/v H2O2) were
198 prepared for the pretreatment of 1 g of rice husks with a solid loading of 2.0% (w/v). This means that
199 1 g of rice husk was added to 50 mL of the solution containing the alkaline peroxide solutions
200 (equivalent to 20 g/L). The mixture was agitated continuously at 150 rpm and the temperature was
201 set to the desired degree of 20°C, 50°C, or 80°C. For all experiments, the reaction time was set at 2hr
202 similar to previously reported studies in the literature (Díaz et al., 2014). The solid residue samples
203 were collected and stored in an oven for 24 h and finally weighed. The concentrations of ash and
204 lignin were obtained from the treated residues. The experiments were carried out in triplicate.
205
207 The percentage of acid-insoluble lignin can be specified as the residue, corrected for acid-insoluble
208 ash, remaining on a standard medium porosity filter crucible after primary (72%) and secondary (4%)
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209 sulfuric acid hydrolysis treatment. The acid-soluble lignin is defined as the portion of the lignin that
210 dissolves during 72% sulfuric acid hydrolysis. Experiments were carried out with the method of
211 (Sluiter et al., 2012). In summary, the samples are first weighed and 72% sulfuric acid is added,
212 followed by being placed in pressure tubes and stirred for hydrolysis for 60 minutes. The acid is then
213 diluted to 4% for the remainder of the test. A UV-Visible spectrophotometer is used to calculate the
214 lignin content, run on a background of deionized water or 4% sulfuric acid. The combination of
215 acid-soluble and acid-insoluble lignin make up the total lignin concentration.
216
218 The ash content was measured using thermogravimetric analysis (TGA) by heating the samples to
219 650°C under an air atmosphere until constant weight was achieved after an extended period (no more
220 than 6 hours). Then the residue is weighed to measure the ash content. Elemental oxides, namely, Al,
221 K, P, Ca, Mg, Na and Fe were only present in minute quantities, the overwhelming amount of the ash
222 was silica dioxide (SiO2). If the precise silica content is wanted, the residue could be washed with
223 HCl. According to a previous study conducted by Bazargan et. al (2015), the rice husk ash mainly
224 comprised silicon (84.1% by weight), followed by potassium (9.4% w/w), and calcium (3.2% w/w)
225 (Bazargan et al., 2015). Under the alkaline conditions experienced in this study, the potassium oxide,
226 carbonate, nitrate, and sulfate are soluble and hence can be removed in the solution.
227
229 The Box-Behnken statistical design (BBD) of the Design Expert 8.06 software was used for the
230 design of experiments and the analysis of results. The independent variables were selected as: NaOH
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231 concentration (X1), H2O2 concentration (X2) and temperature (X3). The quantities of lignin (%), ash
232 removed (%) and solid yield (%) were used as response variables. The low, center, and high levels of
234
Factor Material Units Low Actual Value Center Actual Value High Actual Value
X3 Temperature °C 20 50 80
236
237 A total number of 17 experiments including 5 central points were tabulated (each carried out in
238 triplicate). A polynomial equation was applied to define the relationships between the variables and
240 Y = + ∑ + ∑ + ∑ ∑ (1)
241 Where, Y is the response (percent lignin removal, percent silica removal or percent solid yield). Xi
242 and Xj are the independent variables, β0 is the offset coefficient, βi is the linear effect, βii is the
244
245 Analysis of variance (ANOVA) is a statistical method for detecting differences between groups of
246 samples (Demir Delil et al., 2019). In essence, when used alongside RSM, the ANOVA method
247 compares a continued response across the levels of the tested factors. RSM and ANOVA are
248 functional statistical tools used to determine the optimum conditions, which can later be used to scale
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249 up laboratory experiments to industrial scale implementation (Hossain et al., 2019).
250
251 By applying RSM designs, the performance of a set of assigned independent variables on specified
252 response variables can be statistically validated. One of the added advantages is that by conducting a
253 limited number of experiments, statistically significant relationships can be discerned. With such
254 effectiveness and popularity, RSM has been widely adopted in different fields (Khoshnam et al.,
255 2019).
256
259 The constituents of the rice husks are presented in Table 2. The cellulose content is 31.13% and the
260 hemicellulose content is 17.71%. The 28.25% lignin concentration consists of 3.36% acid soluble
261 lignin and 24.89% acid insoluble lignin. Extractives eliminated in the first step are 5.01%.
262 Meanwhile, the ash content is 16.5% in the husks. The measured values in this study, as shown in
263 Table 2, are more or less in accordance with average values reported in the literature.
264
Cellulose 31.13 30 ± 5
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Acid-insoluble lignin 24.89
28.5 ± 2.5
Acid-soluble lignin 3.36
Ash 16.50 16 ± 1
266
268 In our case, a 3-factor, 3-level BBD is used to evaluate the delignification effect of AHP. The
269 experimental conditions and results for each run are displayed in Table 3. As will be seen, the
270 experimental results closely resembled those predicted by the model. The lignin removal percentages
271 are between 47.93 and 87.93, the silica removal percentages are between 64.40 and 100, and the
272 percentages for solid yield are between 35.91 and 68.16. The data were verified several times, and
274
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6 8 5 50 81.25 96 40.92
17 2 5 50 63 77.15 59.98
276
277
278 By using the response matrix alongside Table 1 and Equation 1, the final response equations, using
279 coded factors (ranging from -1 to 1) become the following in which X1, X2, and X3 are NaOH
281
282 % percent lignin removal = 68.80 + 10.55 + 4.82 + 8.95( − 0.71 − 2.91 ( +
284
285 % percent ash removal = 83.15 + 10.31 + 3.96 + 8.41( − 0.81 − 3.27 ( +
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286 1.00 ( + 0.26 − 0.18 + 2.05( ( 3)
287
289 50.05 − 8.97 − 3.77 − 7.87( − 0.24 + 2.5 ( − 0.65 ( + 1.40 + 1.73 −
290 1.91( ( 4)
291
292 The ANOVA test results for lignin removal, silica ash removal and solid yield are listed in Table 4 (a),
293 (b) and (c) respectively. It is evident, that all F-values of the three responses for the quadratic model
294 imply that the model is significant. Likewise, since the p-value for a particular coefficient is
295 significant when it is smaller than 0.05, it can be concluded that all the parameters studied in this
296 investigation have significant effects on delignification, silica removal and solid yield (Zarei et al.,
297 2019). The coefficients that are not significant shall be removed from the final optimization models.
298 All the lack of fit tests were significant, which is a desirable outcome. For the percent lignin removal,
299 percent ash removal and percent solid yield, there is only a 0.01% chance, a 2.85% chance and a 0.26%
300 chance, respectively, that a lack of fit F-value could occur due to noise. The experimental data
301 satisfactorily fit the model as is also evident from the high R2 values obtained.
302
303 It is important to note that the CV% is a measure obtained by expressing the standard deviation as a
304 percentage of the mean. The smaller the CV%, the better the reproducibility of the results. If this
305 value is under 10, as is the case here, it is acceptable. Meanwhile, a low PRESS value implies a
306 better predictability application of the models. The adequate precision measure is more desirable if it
307 is higher (acceptable when greater than 4). This value shows the signal to noise ratio.
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308
significant
significant
significant
significant
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310
significant
significant
significant
significant
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312
significant
significant
significant
314
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315 From Table 4(a), it is clear that the linear coefficients (X1, X2 and X3) as well as one interaction
316 coefficient (X1X3) and one quadratic coefficient (X32) are the most significant for lignin removal. The
317 same is true for ash removal according to Table 4(b). However, in Table 4(c), another quadratic
318 coefficient (X22) is also significant for the total solid yield. Note that X1, X2, and X3 are NaOH
320 For Response 1 (lignin removal), Response 2 (ash removal) and Response 3 (solid yield), the coded
321 coefficients for X1 (10.55, 10.31, -8.97), X2 (4.82, 3.96, -3.77) and X3 (8.95, 8.41, -7.87) indicated
322 that the most significant linear effect is X1, followed by X3 and then by X2. The similarity of the linear
323 coefficient in Response 1 and 2 suggests that the three independent variables have almost the same
324 significant effects on these two responses. Also, for both Response 1 and 2, the quadratic coded
325 coefficient for X32 (2.85, 2.05) has a more significant effect compared with X12 (-0.81, 0.26) and X22
327
328 Based on the results, after removing the insignificant terms indicated in Table 4, the relationships
329 between the three responses and the independent variables in terms of actual factors are given in
330 Equations (5), (6) and (7) in which X1, X2, and X3 are NaOH concentration, peroxide concentration,
332
335 (5)
336
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337 % percent ash removal =
339 (6)
340
343
344 The summary of the model for lignin removal, ash removal and solid yield are presented in Table
345 5(a), (b) and (c) respectively. The quadratic model is the best fitting model for all responses. The
346 regression coefficients (R2) for the quadratic model are above 0.99, which suggests a high degree of
347 accuracy (Kaur et al., 2019). The similarities between adjusted R2 (0.9933, 0.9825, 0.9805) and
348 predicted R2 (0.9535, 0.8912, 0.8684) for Response 1, Response 2 and Response 3 indicate a reliable
350
351 Table 5(a). Model summary statistics for Response 1 (lignin removal)
352
Source Std. Dev. R-Squared Adj Pred PRESS Comments
353
R-Squared R-Squared
354
Linear 2.47 0.9557 0.9455 0.9091 163.32
355
2FI 2.04 0.9769 0.9631 0.8885 200.27
356
Quadratic 0.86 0.9971 0.9933 0.9535 83.45 Suggested
357
Cubic 0.061 1.0000 1.0000 Aliased
358
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359
360 Table 5(b). Model summary statistics for Response 2 (silica ash removal)
R-Squared R-Squared
361
362 Table 5(c). Model summary statistics for Response 3 (solid yield)
365
Linear 2.37 0.9451 0.9324 0.8866 150.41
366
2FI 2.14 0.9653 0.9446 0.8282 227.80
369
371 Prior to optimization of the process, the adequacy of the quadratic regression model should be
372 checked to avoid inaccurate results. The normal probability plots, the plots of internally studentized
373 residues vs. predicted, and the plots for model precision for Response 1 (lignin removal), Response 2
374 (ash removal) and Response 3 (solid yield) are shown in Figures 1, 2 and 3, respectively. The
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375 linearity of the normal probability plots confirms that the error terms are normally distributed and so
376 the assumptions of the model are supported. Since the randomly scattered points are within the range
377 of ±3.0 in the plot of residual values against the predicted response, the adequacy of the fitted
378 empirical model can be concluded. Moreover, the actual values are in satisfactory agreement with the
379 predicted data, which suggest an acceptable level of precision of the model. Hence, the adequacies of
380 the developed models for predicting lignin removal, ash removal and solid yield have been
381 confirmed.
382
383
384
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385
386
387 Figure 1: (a) Normal probability plot, (b) plot of predicted vs. actual, and, (c) plot of the model
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389
390
391
392
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393
394 Figure 2: (a) Normal probability plot, (b) plot of predicted vs. actual, and, (c) plot of the model
396
397
398
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399
400
401 Figure 3: (a) Normal probability plot, (b) plot of predicted vs. actual, and, (c) plot of the model
403
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404 4.4 Response surfaces
405 The three-dimensional response surface is a great tool for multivariate optimization, by evaluating
406 the interactions between all the factors involved (Azadegan et al., 2019). The effects of NaOH and
407 H2O2 on lignin removal, ash removal, and solid yield are demonstrated by the plots within the ranges
408 of the independent variables. The importance of mutual interactions between all these independent
409 variables can be discerned from the geometry of the plots (Yadav et al., 2019). In the following
410 figures, three response surfaces (correlations) for each response were plotted presenting the effects of
411 three independent variables on lignin removal, ash removal, and solid yield.
412 Figure 4 shows three-dimensional response surfaces for lignin removal. In Figure 4(a), the
413 relationship between the concentration of NaOH and H2O2 on the delignification effect at the center
414 level of lignin removal temperature indicates that with the increase of NaOH and H2O2
415 concentrations, the lignin content in treated rice husks decreases. However, the figure reveals that
416 NaOH has a stronger effect than H2O2 on lignin removal. Figure 4(b) depicts the response surface
417 relationships between temperature and NaOH concentration on delignification at the center level of
418 the H2O2 content. Both NaOH concentration and temperature have an increasing effect on
419 delignification. Increased temperatures show a slight positive effect on delignification at lower
420 temperatures; this effect becomes more pronounced as the temperature increases to higher values.
421 The response surface interactions, between temperature and H2O2 concentration at the center level of
422 NaOH concentration, are displayed in Figure 4(c), which reveals that both temperature and H2O2
424 As can be seen from Figure 4, the increase in temperature results in a higher removal of lignin. This
425 observation is ubiquitous for all concentrations of NaOH or H2O2. The reason for this observation is
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426 that in the presence of reactive chemicals, a higher temperature leads to a more effective breakage of
427 bonds in the lignin structure. This is in accordance with previous findings reported in the literature.
428 For example, 20% higher delignification was seen in the isolation of hemicellulose from corn fiber
429 by alkaline hydrogen peroxide extraction as the temperature was increased from 25°C to 60°C. As
430 the temperatures increased, various different reactions may take place. For example, chromophores
431 may be generated by reducing end groups on the polysaccharide by alkali catalysis (Doner and Hicks,
432 1997). However, it is important to note that higher temperatures do not necessarily mean higher
433 release of total reducing sugars and glucose in the enzymatic hydrolysis (Dutra et al., 2018).
434
435
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436
437
439
440 Figure 5 shows the three-dimensional response surfaces for ash removal. In Figure 5(a), the
441 interaction between NaOH and H2O2 concentrations on ash removal at the center level of
442 temperature indicates that with the increase of NaOH and H2O2 concentrations, the ash content of the
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443 rice husks decreases. However, the effect of H2O2 on ash removal is not as strong as the influence of
444 NaOH. Perhaps this can be ascribed to the formation of sodium silicates (A. Bazargan et al., 2014).
445 Figure 5(b) presents the combined interrelationships between temperature and NaOH concentration
446 on ash removal at the center level of the H2O2 concentration. Both NaOH concentration and
447 temperature have an increasing effect on ash removal. The performance of temperature on ash
448 removal exhibits the same trend as that on lignin removal. The cumulative effect of temperature and
449 H2O2 content at the center level of NaOH concentration are displayed in Figure 5(c), which reveals
450 that both temperature and H2O2 have a significant effect on ash removal.
451 The concentration of hydrogen peroxide is a deciding factor regarding the economic feasibility of
452 AHP treatment. This is because the cost of hydrogen peroxide is considerably more than the value of
453 the biomass and the subsequent products of biorefining, for example ethanol. The obtained results
454 can be compared to a study in which the influence the H2O2 concentration on the release of sugars
455 after enzymatic hydrolysis with cellulase, β -glucosidase, and xylanase was investigated (Saha and
456 Cotta, 2007). In the said study, the increase in peroxide concentration up to 7.5% v/v resulted in
457 increased release of sugars from rice husks but as the concentration increased further (to 10% v/v),
458 the release of sugars was reduced. It has been speculated that the increase of H2O2 beyond an
459 optimum concentration might lead to the formation of inhibitors and the degradation of sugars (Dutra
461
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462
463
Page 33 of 51
464
466
467 Likewise, the response surfaces for solid yield are shown in Figure 6. From Figure 6(a), the
468 interactive effects of NaOH and H2O2 concentration on the ash removal at the center level of
469 temperature suggest that the total solid yield decreases with the increase of NaOH and H2O2
470 concentration. Evidently, NaOH concentration is the main threat to a final high solid yield, compared
471 with H2O2. Figure 6(b) presents the combined effects of temperature and NaOH concentration on
472 total solid yield at the center level of the H2O2 concentration. Previous studies have also
473 demonstrated that a higher temperature has an accelerating effect on lignin removal (Ndazi et al.,
474 2008). With the increase of NaOH concentration and temperature, the final solid yield decreases. The
475 cumulative effects of temperature and H2O2 content at the center level of NaOH content are
476 displayed in Figure 6(c), which reveals that both temperature and H2O2 have a significant effect on
477 ash removal. Hence, it can be concluded from Figures 4, 5 and 6 that the degree of combined
478 interactions with different independent variables in this study are significant on lignin removal, ash
Page 34 of 51
479 removal and solid yield.
480 The concentration of sodium hydroxide has a direct effect on the solution pH. Previous studies have
481 shown that the pH at which AHP treatment takes place is critically important on the results.
482 Generally, a pH of 11.5 is considered optimum, however, some studies have shown lower optimum
483 values (Dutra et al., 2018). That is why it is proposed to carry out optimization studies separately for
484 each biomass. Importantly, it has been shown that using hydrogen peroxide without NaOH results in
485 low efficiency in the release of sugars during enzymatic hydrolysis. For example, in one study
486 executing AHP treatment on aquatic plants, treatment with H2O2 alone was not effective in
487 improving enzymatic hydrolysis. However, when NaOH was used in combination with hydrogen
488 peroxide, excellent enzymatic hydrolysis results were obtained (Mishima et al., 2006).
489
490
491
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492
493
494
496
497 5. Optimization
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498 To obtain the optimized conditions for this study, the balance of lignin, ash removal and final solid
499 yield need to be considered together. In detail, the optimized condition can lead to maximizing the
500 removal of lignin and ash, while leaving behind a sizable amount of final solid residue. The five
501 desirable goals are listed as: none, maximum, minimum, target and in range, for the independent
502 variables and all the responses are provided by the Design Expert software. Two criteria are
503 considered: (a) Maximum lignin and silica removal and solid yield. (b) Maximum lignin and ash
504 removal and solid yield, under the conditions of minimum NaOH and H2O2 concentration and
505 temperature.
506 Under conditions (a), the purpose of this optimization is to find the best reaction conditions with a
507 high solid yield, regardless of the operational costs. The best local maximum for the experimental
508 design was found at 8% NaOH, 1% H2O2 and 20 °C as listed in Table 6. Under such conditions, the
509 predicted lignin removal, ash removal and solid yield are 71.61%, 88.32% and 51.04%, respectively,
510 and the validated experimental results of 71.78% lignin removal, 88.47% silica removal and 50.89%
511 solid yield have confirmed the reliability of the predicted value.
512 Condition (b) however, can be used when a reduction of chemical costs is of importance. Here, the
513 optimized conditions are 5.29% NaOH, 1% H2O2 and 20 °C, with a predicted removal of 59.63% for
514 lignin, 75.06% for silica, and a solid yield of 59.79% as shown in Table 6. The experimental results
515 of 59.85% lignin removal, 75.13% ash removal and 59.21% solid yield are very close to the
516 predicted RSM optimum values. With the estimation of the regression function, the acquired value of
517 desirability was confirmed by the verification of the experimental model and desired condition.
518
519 The amount of lignin remaining after treatment (b) is approximately 40% and the amount of silica
Page 37 of 51
520 remaining is around 25%. The considerable removal of silica can have the benefit of reducing slag
522
523 In order to treat each kilogram of husk, 50 L of solution has been used and this means that per ton of
524 husk, 50 m3 of solution would be required. A reduction of NaOH concentration from 8% (condition a)
525 to 5.29% (condition b) thus corresponds to a reduction from 4 tons to 2.645 tons of NaOH required
526 per ton of husk. Considering the wholesale price of NaOH at $400-600 (99% purity, flake,
527 chembid.com) this means a reduction of NaOH costs from $1600-2400 to $1058-1587 per ton of
528 husk, i.e. a reduction of about 33% in NaOH costs. In future studies, the solid loading rate will also
529 need to be optimized alongside the use of chemicals, to possibly reduce costs even further.
530
531 Table 6. The optimized parameters based on two conditions (a) and (b)
H2O2 (w/v) 1 1
Temperature (°C) 20 20
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532
534 The disruption of the carbohydrate matrix in lignocellulosic biomass is vital for improved
535 fermentation reactions downstream. Ultimately, the recalcitrant structure should be disintegrated into
536 lower molecular weight structures such as monosaccharides, organic acids, and phenolic compounds.
537 The breakdown of the complex polymer matrix is the main issue for effective utilization of
538 lignocellulosic biomass to date (Ho et al., 2019). A considerable amount of research has repeatedly
539 confirmed that the rate and extent of enzymatic hydrolysis are proportional to reduced lignin content
540 in biomass (Akinosho et al., 2017). That is, the lower the lignin content, the higher the microbial
542
543 For more than 40 years, countless studies have demonstrated that the cell wall of biomass can be
544 broken under alkali conditions by hydrolyzing the uronic and acetic acid esters existing in the
545 lignocellulosic matrix, resulting in the elimination of lignin, hemicellulose and silica, and the
546 swelling of cellulose (Jackson, 1977). With the increase of alkaline concentration, the hydrogen bond
547 of cellulose can be disrupted, leading to an increasing number of accessible glycosidic linkages.
548 Hemicelluloses consist of a variety of sugar units and are more reactive than cellulose, which makes
549 the degradation easier and more extensive than cellulose. As a cementing agent, the removal of lignin
550 does not affect the diameter of the rice husk fibers. Without lignin, enzymes become more accessible
551 to the sugars during fermentation. Also, the surface of alkaline treated rice husk becomes rough (as
552 witnessed under the microscope but not reported here), because of the dissolution of the outer layer
553 structures such as hemicellulose, lignin and silica. The removal of silica under alkali conditions is
Page 39 of 51
554 performed through the formation of sodium silicate, which in contrast to silica, is soluble in water
555 (Alireza Bazargan et al., 2014). With the removal of silica, the operational issues downstream such as
557
558 In the current study, the experimental results showed that hydrogen peroxide becomes a more
559 powerful agent for lignin and silica removal under alkaline conditions (refer to figures 4-6). This is
560 in line with previous studies which have shown that under non-alkaline conditions, hydrogen
561 peroxide reacts with only the aliphatic constituents of lignin, and no changes and degradation of
562 phenolic compounds were observed (Sun et al., 2000). In other words, alkali conditions are required
563 for the hydrogen peroxide to attack the phenolic compounds, when phenolic rings are exposed and
564 carboxylic groups are added to the macromolecular structure (Maziero et al., 2012).
565
566 As the pH is increased to about 11.5-11.6, which is the pKa for the H2O2, decomposition reaction, the
567 hydrogen peroxide will dissociate to produce hydroperoxyl anions which are responsible for
568 oxidative reactions of ethylene and carbonyl groups, as well as initiation of radical formation
569 (hydroxyl radicals and superoxide anion radicals). Since all NaOH concentrations used in the current
570 study lead to pH values above 11.5, under all conditions the suitable decomposition will occur. It is
571 speculated (as per the literature) that if lower NaOH concentrations were used, the amount of lignin
573
574 Compared to the current study, other authors have sometimes been able to obtain higher lignin
575 removal percentages through AHP treatment. One of the reasons why the lignin removal from rice
Page 40 of 51
576 husk with AHP might be slightly less than lignin removal from other biomass may be explained by
577 the fact that sodium silicate may act as a stabilizer which may inhibit the decomposition of the
578 hydrogen peroxide (Mittal et al., 2017). Another reason many be the long treatment durations
579 employed in some other studies. For example, in one study 6 hours of treatment with AHP (4.3%
580 hydrogen peroxide concentration) leads to lignin removals above 90%. When reaction duration was
581 extended to 24 hours, and solid loading rates were reduced, the lignin removal surpassed 96%
582 (Correia et al., 2013). Nonetheless, other studies have also reported much lower lignin removal
583 percentages even when reactions durations as long as 48 hours were used, or even when
584 ultrasonication or catalysts were used to improve AHP reactions (Li et al., 2016, 2013). So, it can be
585 stated that the particular characteristics of the biomass will play a considerable role in AHP treatment
586 effectiveness.
587
588 A novel finding of the current study, which may have not been reported elsewhere is that the
589 presence of hydrogen peroxide is not necessarily a good choice if silica removal and high yields are
590 the only two responses. In a previous study by the authors, ash removal of 84.4% and solid yield of
591 79.7% was obtained with 9.8% sodium hydroxide treatment at 44.3C for 22.5 hours without the use
592 of hydrogen peroxide. This shows that if removing the unwanted silica ash while retaining as much
593 solid yield as possible is the goal, given enough residence time, there seems to be no need for
594 employing hydrogen peroxide (Bazargan et al., 2015). The removal of silica from rice husks with
595 sodium hydroxide is thought to occur to the formation of Na2SiO3. In other words, ultimately if
596 adequate reaction time is available, the use of H2O2 alongside NaOH mostly helps the process of
Page 41 of 51
598
599 4. Conclusion
600 The effectiveness of alkaline peroxide pretreatment on rice husks for the removal of lignin and silica
601 ash while retaining a high solid yield has been investigated in this study. The elimination of lignin
602 and ash can resolve the issues regarding the accessibility of enzymes to sugars during fermentation.
603 The removal of the ash component, which mainly contains silica, can also relieve operational
604 problems. The influence of the impurities present in biomass on fermentation reactions is a topic
605 warranting further research. Here, RSM with a BBD has been used to study three independent
606 variables of NaOH and H2O2 concentration and temperature on three responses of lignin and ash
608 The effectiveness of the designed experiment suggests that with alkaline peroxide treatment, rice
609 husks can be transformed into a more suitable resource for biofuel production. During
610 experimentation it was witnessed that as the concentration of hydrogen peroxide and sodium
611 hydroxide increased, the lignin removal and silica ash removal were improved. However, this was at
612 the expense of losing the solid content of the husks. Meanwhile, when compared to previous studies,
613 it was noticed that comparable silica ash removal is possible with less loss of solids if only sodium
614 hydroxide is used (as opposed to hydrogen peroxide plus sodium hydroxide). This may be due to
615 consumption of the alkali by peroxide molecules rather than forming soluble sodium silicate from the
616 husk. Nonetheless, the removal of lignin from the husks is effectual in the presence of H2O2.
617 Two optimized conditions are suggested for maximizing lignin and ash removal while minimizing
618 solid loss. When emphasizing the effectiveness of the reaction, the optimized conditions are 8%
619 NaOH, 1% H2O2 and 20 °C. When chemical cost optimization is of importance, the optimized
Page 42 of 51
620 process parameters become 5.29% NaOH, 1% H2O2 and 20 °C. This would translate into a reduction
621 of 33% in NaOH costs per ton of treated rice husk (approximately $540-800 saved per ton of treated
622 husk).
623
Page 43 of 51
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Declaration of interests
☒ 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.
☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:
Alireza Bazargan
Conceptualization; validation; formal analysis; writing - review & editing; supervision; project
administration;
John P. Barford
resources;
Junaid Saleem
project administration;
Gordon McKay