CN113462727B - Method for pretreatment of protein wastewater based on pH adjustment to improve AD methanogenesis efficiency - Google Patents
Method for pretreatment of protein wastewater based on pH adjustment to improve AD methanogenesis efficiency Download PDFInfo
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Abstract
The invention discloses a method for improving AD methanogenesis efficiency based on pH adjustment pretreatment of protein wastewater, which comprises the following steps: step 1: centrifuging the anaerobic granular sludge, and cleaning the anaerobic granular sludge by using distilled water to obtain centrifugal granular sludge for later use; step 2: the protein wastewater is pretreated by acid or alkali, the pH value of the protein wastewater is regulated, and the protein wastewater after the pH pretreatment is obtained by shaking in an air bath table; step 3: readjusting the pH pretreated protein wastewater to a neutral initial value to obtain neutral protein wastewater; then neutral protein waste water, trace element stock solution and Na 2 HPO 4 、NaHCO 3 And placing the centrifugal granular sludge into a reaction tank for mixing, and then shaking the reaction tank on a shaking table for anaerobic digestion to collect and produce methane. The method of the invention pretreats the protein wastewater by adjusting the pH value to develop the conformation and structure of the protein, thereby eliminating the limit of low methanation rate of the protein wastewater in the AD process.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a method for improving AD methane production efficiency based on pH adjustment pretreatment of protein wastewater
Background
High concentration organic wastewater from slaughterhouses, fish, whey, casein, cheese and certain vegetable processing processes typically contains large amounts of proteins with high energy densities and no neglect of bioavailable value. For example, over 40% of the total chemical oxygen demand in dairy wastewater is derived from proteins, and how to efficiently treat and utilize such high protein wastewater is a current challenge for sewage treatment plants. Considering that high protein wastewater is rich in biodegradable organic nutrients, a great deal of research on bioconversion of such wastewater by biological methods has been conducted. From the conventional point of view, the aerobic biological treatment method is difficult to cope with high concentration organic matters in wastewater, and suffers from high load impact, so that the operation stability of the reactor is deteriorated. At the same time, the aerobic biological treatment unit needs to additionally supply oxygen, which leads to further increase of the operation cost. In contrast, the anaerobic biological treatment method not only avoids the defects of the aerobic biological treatment method, but also can effectively recover energy, so that the anaerobic biological treatment method becomes an ideal technology for treating high-concentration organic wastewater. Proteins with higher energy densities possess significant biogas production potential compared to carbohydrates such as glucose, crop residues and livestock manure, measured by the amount of organic matter in Chemical Oxygen Demand (COD) quantified waste streams. According to the Buswell equation, the theoretical methane yield per unit COD at standard temperature and pressure is 0.35L, the conversion coefficient of protein to COD is 1.5, and the carbohydrate is only 1.07. Therefore, it is important to study the process and efficiency of protein bioconversion to methane in Anaerobic Digestion (AD) systems.
AD is a process of biologically converting complex high-concentration organic wastewater into alternative clean energy sources through the mutual cooperation of a plurality of functional bacteria under anaerobic or anoxic conditions to form a metabolic microenvironment. AD is generally summarized in the following three steps: hydrolytic acidification, acetylation, and methanogenesis. In particular, proteins are natural polymers formed from amino acid units that are linked to each other by peptide bonds (or amides). The protein is first hydrolyzed by extracellular enzymes (called proteases) to oligomeric polypeptides and monomeric amino acids before being converted to methane by functional bacteria. Thereafter, an amino groupWhich way the acid enters the fermentation stage depends on the nature and concentration of the monomeric amino acid. However, the actual rate of proteolysis is rather slow, and the methane yield of AD is much lower (less than 0.5L CH 4 /g protein) due to the system disturbances caused by the direct impact of large amounts of high-load protein wastewater and the increased risk of ammonia inhibition by anaerobic microorganisms. Recent work has found that the stability and complexity of the protein structure is another important factor that hinders methanation, because proteins have three-dimensional structures, multilayer conformations that make them less susceptible to cleavage by proteases in native folding, such as stable hydrogen bonding networks. Therefore, the adoption of proper pretreatment means is important for removing the limit of the hydrolysis rate of protein wastewater in the AD methanation process.
In recent years, physical and chemical methods such as acid, alkali, heat, ultrasonic waves and ultraviolet rays are applied to pretreatment processes of protein-rich biomass such as sewage or sludge, so that dissolution of extracellular polymers in the sludge and disruption of cell walls are promoted, a large amount of intracellular organic substances are released, and methane production is further promoted. However, the complexity of biomass composition and the diversity of organic monomer sources after hydrolysis make it quite difficult to establish a direct link between AD methanogenic properties and biomass components, which can only be simply estimated using theoretical contributions. Based on this consideration, it is logical to explore the conversion relationship between the hydrolysis product and the methanogenic efficiency by pre-treating a single organic material, such as a protein. Numerous studies have shown that proteolysis can be accelerated by protein denaturation, but these reports are mostly focused on the conversion of protein wastewater to hydrogen or VFAs in AD systems. Thus, the inherent relationship and mechanisms between the unfolding of the proteolytic conformation and structure and the strengthening of the hydrolysis and methanogenesis processes remain blank.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for improving AD methanogenesis efficiency by adjusting pH to pretreat protein wastewater.
The technical scheme of the invention is as follows: a method for pretreatment of protein wastewater based on pH adjustment to improve AD methanogenesis efficiency, comprising the steps of:
step 1: microbial preparation
Centrifuging the anaerobic granular sludge at 12000rpm for 10min, removing soluble organic matters, and cleaning for 2 times by using distilled water to obtain centrifugal granular sludge for later use;
step 2: pH pretreatment
The protein wastewater is subjected to pH adjustment treatment to change the pH value of the protein wastewater, and is rocked in an air bath cradle at room temperature for 6-24 hours to obtain protein wastewater after pH pretreatment;
step 3: anaerobic digestion
1) The protein wastewater after the pH pretreatment is readjusted to a pH neutral initial value to obtain neutral protein wastewater;
2) Then according to 150mL neutral protein wastewater, 1mL trace element stock solution and 0.3g Na 2 HPO 4 、1g NaHCO 3 15g of centrifugal granular sludge is placed in a reaction tank for mixing, and helium is introduced to empty oxygen in the reaction tank, so that the anaerobic environment in the reaction tank is ensured;
3) Then, the temperature in the reaction tank was controlled at 35.+ -. 1 ℃ and anaerobic digestion was carried out on a shaker at a shaking speed of 120rpm, and methane was collected.
The invention can develop the conformation and structure of the protein by adopting pH to pretreat the wastewater, thereby eliminating the limit of low methanation rate of the protein wastewater in the AD process.
Further, the pH adjustment treatment in step S2 specifically includes: the pH of the protein wastewater is adjusted to 2-6 by adopting acid pretreatment, namely 4M hydrochloric acid. The protein wastewater is pretreated through acidic pretreatment, so that the conformation and structure of the protein are unfolded, and the limit of low methanation rate of the protein wastewater in the AD process is eliminated.
Further, the pH adjustment treatment in step S2 specifically includes: alkaline pretreatment is adopted, namely the pH value of the protein wastewater is adjusted to 8-12 by 4M sodium hydroxide. Alkaline pretreatment, especially at ph=12, significantly increased methane production by 35.7% relative to the non-pH pretreatment process to 149.6±16.1ml/g protein; this is due to breakdown of the hydrogen bond network caused by c=o stretching vibration of the amide I band, which causes a transition from ordered to disordered secondary structure of the protein; however, time economic evaluation shows that the best solution for alkaline pretreatment of protein wastewater (ph=12) requires a tradeoff between time benefit and methane yield benefit.
Further, the air bath cradle in the step S2 specifically comprises: shaking was performed at a shaking speed of 100rpm at room temperature of 25 ℃. The pH pretreatment can be fully performed on the protein wastewater through the temperature and the shaking speed, so that the treatment effect of the pH pretreatment on the protein wastewater is ensured.
Further, in the step S2, before the protein wastewater is subjected to the pH pretreatment, the protein wastewater is subjected to the variable power microwave pretreatment by varying the temperature in the range of 20 to 30 ℃, wherein the microwave frequency is 2 to 3GHz. The protein can be rapidly hydrolyzed into amino acid by microwave hydrolysis, and the microwave can promote the secondary conformational change of the protein to different degrees, so that the protein hydrolysis is promoted, and after the complex structure of the protein is simplified, the protein is beneficial to the subsequent metabolic decomposition process such as anaerobic digestion and metabolism, and the hydrolysis and acidification steps of protein waste water are greatly shortened, so that the recycling utilization efficiency of the protein waste water is improved.
Further, the variable parameter variation of the microwave power satisfies the formula (1), specifically as follows:
P＝4C·f 2 (1)
wherein C represents the temperature of protein wastewater, P represents the microwave power of microwave pretreatment, and f represents the microwave frequency of the microwave pretreatment. According to research, the influence of different temperatures, microwave power and microwave frequency on the promotion of the secondary conformational change of proteins in protein wastewater is different, and the microwave pretreatment effect is kept to be higher by adaptively adjusting and changing along with the temperature environment, so that the subsequent methane production efficiency of AD is improved.
Further, the mixing manner in the step S3 specifically includes: adding mixed slurry of gelatin coated high-carbon steel balls and 15g centrifugal granular sludge into 150mL neutral protein wastewater, wherein the mixed slurry comprisesThe gelatin coated high-carbon steel ball accounts for 20-30% of the total volume of the neutral protein wastewater, wherein 1mL of trace element stock solution and 1g of NaHCO are added into a mixed gelatin layer adopting the gelatin coated high-carbon steel ball 3 0.3g Na 2 HPO 4 . By using gelatin to contain trace element stock solution and Na 2 HPO 4 Can be slowly released into neutral protein water body, thereby maintaining the long-acting anaerobic fermentation treatment efficiency.
Furthermore, the mixed slurry needs to be mixed with gelatin coated high-carbon steel balls and centrifugal granular sludge and stirred for 15min under the magnetic field strength of 0.1-0.2T before being put into neutral protein wastewater. The magnetic field intensity in the range is added for treatment, so that the centrifugal granular sludge is magnetically activated to improve the microbial activity, the gelatin-coated high-carbon steel balls can be magnetized, the high-carbon steel characteristics of the gelatin-coated high-carbon steel balls are utilized for storing magnetism for a long time, and when the gelatin-coated high-carbon steel balls are put into the central protein wastewater, the microbial activity can be effectively promoted, the neutral protein wastewater water body can be magnetized to influence, and the anaerobic digestion treatment of the neutral protein wastewater is promoted.
Furthermore, the preparation method of the gelatin coated high-carbon steel ball specifically comprises the following steps: selecting high-carbon steel balls with particle size of 1+/-0.1 cm, specifically, storing microelement stock solution and NaHCO 3 Na (sodium carbonate) 2 HPO 4 Mixing with gelatin to obtain mixed gelatin, and coating the mixed gelatin on the surface of high carbon steel beads to make the thickness of the mixed gelatin coated on the high carbon steel be 0.6+/-0.05 cm. The problems of small adhesion surface of the mixed gelatin layer and the like caused by too small particle size can be avoided by selecting the high-carbon steel balls in the range, and the problems of low magnetizing efficiency and high mass caused by too large particle size are solved, so that rapid sedimentation is very easy; the thickness range of the mixed gelatin can meet the integral duration of anaerobic digestion treatment, and simultaneously, the influence of the excessive thickness of the mixed gelatin layer on the magnetization efficiency and the like is avoided.
The beneficial effects of the invention are as follows:
(1) The method of the invention pretreats the protein wastewater by adjusting the pH value to develop the conformation and structure of the protein, thereby eliminating the limit of low methanation rate of the protein wastewater in the AD process.
(2) The invention provides various schemes for adjusting the protein wastewater by pH value, and the optimal scheme for adjusting the protein wastewater by pH value can be selected according to the trade-off between the time benefit and the methane yield rate benefit.
(3) The invention provides a microwave pretreatment method, and adjusts microwave power and microwave frequency according to the change temperature, thereby improving the effect of promoting the secondary conformational change of protein in protein wastewater, and further improving the subsequent AD methane production efficiency.
(4) The invention provides a mode of adding components of anaerobic digestion, which comprises a trace element stock solution and NaHCO by adopting gelatin 3 Na (sodium carbonate) 2 HPO 4 Can be slowly released into neutral protein water body, so as to maintain the long-acting anaerobic fermentation treatment efficiency, and simultaneously, the high-carbon steel magnetization is utilized to promote the microbial activity for a long time, and the magnetization influences the neutral protein wastewater water body, thereby improving the anaerobic digestion treatment effect of the neutral protein wastewater.
Drawings
FIG. 1 shows methane production rate after 24h pretreatment at different pH values, (A) acidic condition (B) basic condition, (error bars represent standard deviation of triplicate samples);
fig. 2 is methane yield at various pretreatment times (a) ph=3, (B) ph=12, (error bars represent standard deviation of triplicate samples);
FIG. 3 is a graph showing the results of a synchronous fluorescence spectrum analysis of pretreated protein wastewater: (a) a pretreatment time based on ph=3; (B) pretreatment time at ph=12 (ex=292 nm);
FIG. 4 shows the transformation of the secondary structure of proteins, (A-D) far-UV-CD spectra of protein wastewater pretreated with different pH conditions, (a-D) secondary structure composition changes based on CD spectra decoding;
fig. 5 is an infrared spectrum of the protein after acidic and basic pretreatment at optimum pH (a) ph=3 pretreatment for 24h and (B) ph=12 pretreatment for 24h.
Detailed Description
The invention will be described in further detail with reference to the following embodiments to better embody the advantages of the invention.
Example 1
A method for pretreatment of protein wastewater based on pH adjustment to improve AD methanogenesis efficiency, comprising the steps of:
step 1: microbial preparation
Centrifuging the anaerobic granular sludge at 12000rpm for 10min, removing soluble organic matters, and cleaning for 2 times by using distilled water to obtain centrifugal granular sludge for later use;
step 2: pH pretreatment
The protein wastewater is subjected to pH adjustment treatment to change the pH value of the protein wastewater, and is shaken for 18 hours in an air bath cradle at room temperature to obtain protein wastewater after pH pretreatment; the pH adjustment treatment in step S2 specifically includes: the pH of the protein wastewater was adjusted to 3 by acidic pretreatment, i.e., by 4M hydrochloric acid. The protein wastewater is pretreated through acidic pretreatment, so that the conformation and structure of the protein are unfolded, and the limitation of low methanation rate of the protein wastewater in the AD process is eliminated;
the air bath shaking table in the step S2 specifically comprises the following steps: shaking was performed at a shaking speed of 100rpm at room temperature of 25 ℃. The pH pretreatment can be fully performed on the protein wastewater through the temperature and the shaking speed, so that the treatment effect of the pH pretreatment on the protein wastewater is ensured.
Step 3: anaerobic digestion
1) The protein wastewater after the pH pretreatment is readjusted to a pH neutral initial value to obtain neutral protein wastewater;
2) Then according to 150mL neutral protein wastewater, 1mL trace element stock solution and 0.3g Na 2 HPO 4 、1g NaHCO 3 15g of centrifugal granular sludge is placed in a reaction tank for mixing, and helium is introduced to empty oxygen in the reaction tank, so that the anaerobic environment in the reaction tank is ensured;
3) The reaction tank was then controlled at 35℃and anaerobic digestion was carried out on a shaker at a shaking speed of 120rpm, and methane was collected.
The invention can develop the conformation and structure of the protein by adopting pH to pretreat the wastewater, thereby eliminating the limit of low methanation rate of the protein wastewater in the AD process.
Example 2
This example is substantially the same as example 1, except that the pH adjustment treatment in step S2 is specifically: the pH of the protein wastewater was adjusted to 2 by acidic pretreatment, i.e., by 4M hydrochloric acid.
Example 3
This example is substantially the same as example 1, except that the pH adjustment treatment in step S2 is specifically: the pH of the protein wastewater was adjusted to 6 by acidic pretreatment, i.e., by 4M hydrochloric acid.
Example 4
This example is substantially the same as example 1, except that the pH adjustment treatment in step S2 is specifically: alkaline pretreatment, i.e. the pH of the protein wastewater was adjusted to 12 by 4M sodium hydroxide, was used. Alkaline pretreatment, especially at ph=12, significantly increased methane production by 35.7% relative to the process without pH pretreatment, reaching 149.6±16.1ml/g protein; this is due to breakdown of the hydrogen bond network caused by c=o stretching vibration of the amide I band, which causes a transition from ordered to disordered secondary structure of the protein; however, time economic evaluation shows that the best solution for alkaline pretreatment of protein wastewater (ph=12) requires a tradeoff between time benefit and methane yield benefit.
Example 5
This example is substantially the same as example 4, except that the pH adjustment treatment in step S2 is specifically: alkaline pretreatment, i.e. the pH of the protein wastewater was adjusted to 8 by 4M sodium hydroxide, was used.
Example 6
This example is substantially the same as example 4, except that the pH adjustment treatment in step S2 is specifically: alkaline pretreatment, i.e. the pH of the protein wastewater was adjusted to 10 by 4M sodium hydroxide, was used.
Example 7
This example is essentially the same as example 1, except that the pH pretreatment of step S2 is agitated for 6 hours in an air bath shaker.
Example 8
This example is essentially the same as example 1, except that the pH pretreatment of step S2 is agitated in an air bath shaker for 24 hours.
Example 9
This example is basically the same as example 1, except that in the step S2, the protein wastewater is subjected to a variable power microwave pretreatment at a temperature ranging from 25 ℃ before the protein wastewater is subjected to the pH pretreatment, wherein the microwave frequency is 2.8GHz. The protein can be rapidly hydrolyzed into amino acid by microwave hydrolysis, and the microwave can promote the secondary conformational change of the protein to different degrees, so that the protein hydrolysis is promoted, and after the complex structure of the protein is simplified, the protein is beneficial to the subsequent metabolic decomposition process such as anaerobic digestion and metabolism, and the hydrolysis and acidification steps of protein waste water are greatly shortened, so that the recycling utilization efficiency of the protein waste water is improved.
The variable parameter variation of the microwave power satisfies the formula (1), and is specifically as follows:
P＝4C·f 2 (1)
wherein C represents the temperature of protein wastewater, P represents the microwave power of microwave pretreatment, and f represents the microwave frequency of the microwave pretreatment. According to research, the influence of different temperatures, microwave power and microwave frequency on the promotion of the secondary conformational change of protein in protein wastewater is different, and the microwave pretreatment effect is kept to be higher by adapting and changing along with the temperature environment, so that the subsequent methane production efficiency of AD is improved;
the above-mentioned C is 25, f is 2.8, and the result is p=784w, taking formula (1).
Example 10
This example is substantially the same as example 9, except that the parameters of the microwave pretreatment are different, specifically:
the above-mentioned C is 20, f is 2, and the result is p=320W, taking formula (1).
Example 11
This example is substantially the same as example 9, except that the parameters of the microwave pretreatment are different, specifically:
the above-mentioned C is 30, f is 3, and the result is p=1080W, taking formula (1).
Example 12
The present embodiment is basically the same as embodiment 1, except that the mixing manner in step S3 specifically includes: adding mixed slurry of gelatin coated high-carbon steel balls and 15g of centrifugal granular sludge according to 150mL of neutral protein wastewater, wherein the gelatin coated high-carbon steel balls account for 27% of the total volume of the neutral protein wastewater, and a mixed gelatin layer adopting the gelatin coated high-carbon steel balls is added with 1mL of trace element stock solution and 1g of NaHCO 3 0.3g Na 2 HPO 4 . By using gelatin to contain trace element stock solution and Na 2 HPO 4 Can be slowly released into neutral protein water body, thereby maintaining the long-acting anaerobic fermentation treatment efficiency.
Before neutral protein wastewater is added into the mixed slurry, gelatin coated high-carbon steel balls and centrifugal granular sludge are mixed and stirred for 15min under the magnetic field strength of 0.15T. The magnetic field intensity in the range is added for treatment, so that the centrifugal granular sludge is magnetically activated to improve the microbial activity, the gelatin-coated high-carbon steel balls can be magnetized, the high-carbon steel characteristics of the gelatin-coated high-carbon steel balls are utilized for storing magnetism for a long time, and when the gelatin-coated high-carbon steel balls are put into the central protein wastewater, the microbial activity can be effectively promoted, the neutral protein wastewater water body can be magnetized to influence, and the anaerobic digestion treatment of the neutral protein wastewater is promoted.
The preparation method of the gelatin coated high-carbon steel ball specifically comprises the following steps: selecting high-carbon steel balls with the grain diameter of 1cm, specifically, storing microelement stock solution and NaHCO 3 Na (sodium carbonate) 2 HPO 4 Mixing with gelatin to obtain mixed gelatin, and coating the mixed gelatin on the surface of high carbon steel beads to make the thickness of the mixed gelatin coated on the high carbon steel be 0.6cm. The high-carbon steel balls with the above range are selected to avoid the problems of small adhesion surface of the mixed gelatin layer with too small particle size, low magnetizing efficiency with too large particle size and extremely easy rapid sedimentation with too large massThe method comprises the steps of carrying out a first treatment on the surface of the The thickness range of the mixed gelatin can meet the integral duration of anaerobic digestion treatment, and simultaneously, the influence of the excessive thickness of the mixed gelatin layer on the magnetization efficiency and the like is avoided.
Example 13
This example is essentially the same as example 12 except that the gelatin coated high carbon steel beads comprise 20% of the total volume of neutral protein wastewater.
Example 14
This example is essentially the same as example 12 except that the gelatin coated high carbon steel beads comprise 30% of the total volume of neutral protein wastewater.
Example 15
This example is substantially the same as example 12, except that the mixed slurry is mixed with gelatin-coated high carbon steel balls and centrifugal granular sludge and stirred for 15min at a magnetic field strength of 0.1T before being put into neutral protein wastewater.
Example 16
This example is substantially the same as example 12, except that the mixed slurry is mixed with gelatin-coated high carbon steel balls and centrifugal granular sludge and stirred for 15min at a magnetic field strength of 0.2T before being put into neutral protein wastewater.
AD methane production efficiency experiment of protein wastewater
The BSA (bovine serum albumin, available from Equitech-Bio in the United states) is used as a carbon source to prepare synthetic protein wastewater, and the COD set value is kept at 5000mg/L; meanwhile, the anaerobic granular sludge is selected from anaerobic granular sludge obtained in a UASB reactor of a sewage treatment plant in a certain city of Jiangsu in China; the microelement stock solution is Hunter microelement solution;
the methane content in the biogas was determined by gas chromatography (Scientific TM TRACE 1310) equipped with a thermal conductivity detector with nitrogen as carrier gas; circular Dichroism (CD), fluorescence spectroscopy and FTIR spectroscopy were used to describe changes in the secondary structure of proteins; briefly, a JASCO J-715 automated recording spectrophotometer (Tokyo, japan) was used, controlled by JASCO software, using a 0.1cm quartz cell at room temperature to obtain CD lightA spectrum; the pretreated sample was diluted to a concentration of about 45 mg BSA/L and then transferred to a quartz cell having an optical path length of 1 cm; measuring molecular ellipticity in 190-250nm, keeping bandwidth at 1nm and scanning speed at 50nm/min; in the scanning process, each spectrum is automatically corrected according to the selection of distilled water as a blank.
The alpha-helix content is calculated according to the following formulas (2), (3):
wherein MRE is the average residue ellipticity (deg cm) 2 dmol -1 ) CP is the molar concentration of the protein, n is the number of amino acid residues (BSA is 583), L is the path length (mm) of the cell;
wherein MRE is 208 Is the MRE observed at 208nm, 4000 is the MRE of the beta form crossing the random coil conformation at 208nm, 33000 is the MRE value of the pure helix at 208 nm.
Three-dimensional excitation-emission matrix fluorescence spectroscopy and simultaneous fluorescence spectroscopy were used to characterize the luminescence spectroscopy of protein samples (Fluoromax-4 Spectrofluorometer,HORIBA Scientific, france); the sample was first filtered through a 0.45mm hydrophilic filter membrane and then diluted to an approximate concentration prior to testing to avoid exceeding the measurement range of the instrument; in order to obtain a synchronous fluorescence spectrum, the excitation wavelength is from 250 to 450nm, the step length is 5nm, and the offset (delta lambda) is constant at 60nm; fourier infrared spectrum is used for detecting characteristic absorption peaks of functional groups in protein, and scanning range is 500-4000cm -1 。
The following experimental study was now made:
1. the influence of different pH values on AD methanogenesis efficiency of protein wastewater in acid pretreatment is explored
As a test comparison of acidic pretreatment at different pH, examples 1-3 were used, and AD methanogenic properties of protein wastewater pretreated at different pH gradients are shown in FIG. 1A. No significant improvement and group-to-group differences in methane production occurred in the first 12 h. This is because anaerobic granular sludge needs to undergo a short adaptation phase, which does not show differences due to different pretreatment conditions. As shown in FIG. 1A, the methane production rate of the untreated 5g COD/L BSA synthetic wastewater at 120h was 110.2.+ -. 5.1mL/g protein. And after acidic pretreatment, the minimum and maximum methane production rates of the synthetic wastewater at 120h were 125.5.+ -. 2.6mL/g protein (pH=5) and 142.6.+ -. 4.0mL/g protein (pH=3). Methane production rate was increased by 13.9% (ph=5) and 29.4% (ph=3), respectively, compared to the control group, which was not pH pretreated. This may be based on the fact that at low pH the protein molecules will be in an unstable intermediate molten globule state, the conformation of the protein will change and the active parts susceptible to hydrolytic enzymes will be exposed, which will significantly increase the hydrolysis and acidification efficiency of the anaerobic fermentation and thus achieve a better methane production rate.
2. The influence of different pH values on AD methanogenesis efficiency of protein wastewater in alkaline pretreatment is explored
As a test comparison of alkaline pretreatment at different pH in examples 4-6, after pretreatment at alkaline conditions of ph=8-12, as shown in fig. 1B, the results showed that the minimum and maximum methane production rate at 120h was 138.4±3.8mL/g protein (ph=8) and 149.6±16.1mL/g protein (ph=12), respectively, increased by 25.6% and 35.7% compared to the control group (110.2±5.1mL/g protein), which was not subjected to the pH pretreatment. Furthermore, the adaptation of anaerobic fermentation functional bacteria to alkaline pretreated protein wastewater seems to be higher than to acidic pretreatment. In particular, after the anaerobic fermentation had been carried out for 24 hours, a significant difference in methane accumulation was observed, wherein the methane production rates of the pretreated protein wastewater of ph=12 and ph=3 were 47.4±1.4mL/g protein and 16.9±4.2mL/g protein, respectively, and the control group was 13.0±0.9mL/g protein. The rapid increase in methane production rate of alkaline pretreatment protein wastewater continues for up to 60 hours, and then the trend of the increase in the two pretreatment trends to be consistent.
3. The influence of the shaking time of an air bath shaking table in pretreatment of different pH values on the AD methane production efficiency of protein wastewater is explored
The methane production performance of AD was obtained by subjecting the synthetic protein waste water to different pretreatment times (6 h, 12h, 18h and 24 h) with examples 1, 7, 8 as experimental comparisons of different air bath shaker shaking times. As shown in fig. 2A, after 6h of pretreatment at ph=3, the methane production rate can reach 134.3±1.3mL/g protein by methanation process, and 74.4% methane gain effect is achieved compared with the experimental group (142.6±4.0mL/g protein) of pretreatment for 24h. Thus, it is economically desirable to pretreat synthetic protein wastewater for 6 hours under acidic pretreatment (ph=3). Similarly, alkaline pretreatment of synthetic protein wastewater at ph=12 (fig. 2B) showed that methane production rate can reach 142.6±17.3mL/g protein over 120h of methanogenesis at pretreatment time of 6h. Compared with the methane production rate (149.6+/-16.1 mL/g protein) of alkaline pretreatment for 24 hours, the methane gain effect reaches 82.2 percent. Therefore, whether it is an acidic pretreatment or an alkaline pretreatment, it is scientific and reasonable to select a pretreatment time of 6 hours based on economic considerations. In addition, compared with the synthetic wastewater treated by acid, the anaerobic fermentation functional bacteria have better adaptability to the wastewater treated by alkali no matter how long the pretreatment time is.
4. Investigation of the Effect of microwave pretreatment with and without on the methanogenic efficiency of protein wastewater AD
Examples 1, 9 were each measured for methane yield after 120 hours without microwave pretreatment, wherein example 1 produced methane yield after 120 hours was about 142.6.+ -. 4.0mL/g protein, and example 9 produced methane yield after 120 hours was about 151.3.+ -. 8.9mL/g protein; as can be seen by comparison, example 9, which had been pretreated with microwaves, had a higher methane production efficiency than example 1.
5. The influence of different microwave pretreatment parameters on AD methane production efficiency of protein wastewater under microwave pretreatment is explored
Examples 9-11 were each methods under different microwave pretreatment parameters, each of which was measured for methane yield after 120 hours, wherein example 9 produced methane yield after 120 hours was about 151.3.+ -. 8.9mL/g protein, while example 10 produced methane yield after 120 hours was about 149.1.+ -. 7.3mL/g protein, and example 11 produced methane yield after 120 hours was about 152.6.+ -. 9.5mL/g protein; it can be seen that the difference of methane yield in examples 9-11 is not obvious, and a relatively stable methane production efficiency promoting effect can be maintained by dynamically adjusting the microwave pretreatment parameters according to the temperature change through the formula (1);
meanwhile, the pretreatment was carried out by using the microwave power 784W of example 9 based on the temperatures of 20℃and 30℃of examples 10 and 11, and the results were recorded as comparative example 1 and comparative example 2, wherein the methane yield after 120 hours was about 141.3.+ -. 9.1mL/g protein, and the methane yield after 120 hours was about 143.7.+ -. 8.8mL/g protein in comparative example 2, and it was found that the methane production efficiency was somewhat lower in comparative example 1 as compared with example 10 and comparative example 2 as compared with example 11.
6. The influence on the AD methanogenesis efficiency of protein wastewater under different mixing modes in anaerobic digestion is explored
Examples 1 and 12 were respectively prepared by direct mixing and using gelatin coated high carbon steel beads, and the methane yield after 120 hours was measured, wherein the methane yield after 120 hours was about 142.6.+ -. 4.0mL/g protein in example 1, and the methane yield after 120 hours was about 156.5.+ -. 3.7mL/g protein in example 12, and it was found by comparison that example 12 using gelatin coated high carbon steel beads had higher methane production efficiency than example 1;
meanwhile, considering that gelatin was introduced in example 12, the same amount of gelatin as in example 12 was added based on example 1, and this was recorded as control 3, and the methane yield after 120 hours in control 3 was about 145.2.+ -. 5.7mL/g protein, it was seen by comparison that example 12 was still superior to control 3 in which the same amount of gelatin was introduced.
7. The influence of the addition amount of different gelatin coated high-carbon steel balls on the AD methane production efficiency of protein wastewater is explored
Examples 12-14 are methods of adding different gelatin coated high carbon steel balls, and the methane yield after 120h is measured, wherein the methane yield after 120h is about 156.5+/-3.7 mL/g protein in example 12, the methane yield after 120h is about 150.5+/-3.3 mL/g protein in example 13, the methane yield after 120h is about 157.5+/-3.9 mL/g protein in example 14, and the methane yield is obviously increased in the interval of 20-27% of the adding amount, and the methane yield is slowly increased in the interval of 27-30%, so that the adding amount of the gelatin coated high carbon steel balls can be selected according to practical requirements based on the aspects of practical cost and the like.
8. The influence of the treatment of mixed slurry with different magnetic field intensities on the AD methane production efficiency of protein wastewater is explored
Examples 12, 15 and 16 were each methods under different magnetic field strengths, and the methane yield after 120 hours was measured, wherein the methane yield after 120 hours was about 156.5.+ -. 3.7mL/g protein in example 12, and the methane yield after 120 hours was about 152.7.+ -. 3.5mL/g protein in example 13, and the methane yield after 120 hours was about 157.3.+ -. 4.0mL/g protein in example 14, and it was found by comparison that the methane yield increased significantly in the interval of 0.1 to 0.15T and the methane yield increased more slowly in the interval of 0.15 to 0.2T, and therefore, the magnetic field strength of example 12 was selected to be suitable from the economical point of view.
Meanwhile, in order to further explore the influence of pH pretreatment on the AD methanogenesis efficiency of protein wastewater, the endogenous fluorescence characteristics, the secondary structural characteristics of protein and the Fourier transform infrared spectrum of BSA after acid-base pretreatment are explored, and the method is specifically as follows:
1. endogenous fluorescence characteristics of protein wastewater
Endogenous fluorescence of proteins is mainly derived from tryptophan (Trp), tyrosine (Tyr) and phenylalanine (Phe) residues in the molecule. As a protein macromolecule with strong fluorescence, BSA has 2 Trp residues, 21 Tyr residues and 26 Phe residues in each molecule, and all three chromophores have own characteristic fluorescence peaks. Trp residues include Trp 134 and Trp 212, which are located in domain I and domain II, respectively, while fluorescence is predominantly emitted by the Trp residue at position 212. Fluorescence caused only by tryptophan residues can be selectively measured by excitation around 295nm, as tyrosine is not absorbed at this wavelength. In addition, trp residues exhibit higher environmental polarity sensitivity and fluorescence quantum yield than Tyr and Phe residues, thus exerting long-term and productive optical spectral effects in solving the secret of protein conformation and structure.
At an excitation wavelength of 292nm, the maximum emission peak of the Trp residue in the untreated BSA sample was determined to be 345nm, whereas the maximum emission peak of the free L-Trp was at 352nm, resulting in a blue shift of 7nm in the maximum emission wavelength of the Trp residue. This suggests that most Trp residues in BSA are encapsulated inside the molecule and that free contact with water is limited in hydrophobic microenvironments of low polarity. After 24h acidic pretreatment at ph=3, the fluorescent peak position of Trp residues in BSA changed from 345nm to 350nm, resulting in a slight increase in red shift and stokes shift (Δλ). At the same time, the fluorescence intensity at the peak position also decreases significantly, indicating that the microenvironment is changed to a more polar environment, because the Trp residues are exposed from the original hydrophobic cavity inside the molecule. However, under the same conditions, the emission wavelength of the fluorescence peak is slightly smaller than that of the free L-Trp, and the peak position still has a certain blue shift, which indicates that Trp residues in BSA molecules are not completely exposed to water environment after 24h pretreatment with pH=3, and a part of Trp residues still exist in hydrophobic cavities in the molecules.
In contrast, the position of the fluorescence peak of Trp residue in BSA treated for 24h at alkaline condition of ph=12 changed from 345nm to 340nm, blue shift occurred in emission wavelength, and the intensity of the fluorescence peak was reduced by 43.8% (from 122670a.u. Down to 689989 a.u.). The decrease in fluorescence intensity of proteins, and more often, is caused by two factors, one being quenching of fluorescence of the aromatic residues and shifting of the fluorescent peak position, and the other being oxidation of the aromatic residues. From the data, it appears that the decrease in fluorescence intensity is the result of the synergistic effect of the two quenching pathways. Furthermore, an increase in hydrophobicity indicates that Trp residues are located in hydrophobic regions within the protein molecule, which also indicates that the conformation of the protein may have migrated. At other pH conditions, whether acidic or basic, the decrease in fluorescence intensity value may only be caused by oxidation of the aromatic amino acid, not by fluorescence quenching, as there is no blue shift in fluorescence maximum emission.
As shown in fig. 3 and table 1, the fluorescence quenching under acidic pretreatment conditions was attributable to the oxidation of the aromatic amino acid, except for the case where the pretreatment time was 24h, because no significant peak position change was found. Unlike acidic pretreatment, the fluorescence intensity of the protein wastewater from alkaline pretreatment is significantly reduced, probably due to blue shift of the maximum peak of fluorescence at different pretreatment times in terms of emission wave, resulting in fluorescence quenching. Furthermore, alkaline pretreatment tends to significantly alter the conformation and structure of the protein, regardless of the pretreatment time, due to the increased hydrophobicity resulting from blue-shift. Thus, protein denaturation can be achieved with alkaline pretreatment (ph=12) for only 6h.
2. Secondary structural properties of proteins
Proteolysis is the rate limiting step in AD because of the complex conformation and structure of the protein itself, which requires degradation into peptides and amino acids by hydrolytic enzymes to be utilized by methanogens. The secondary structure of primary BSA is mainly an alpha-helix and beta-sheet structure formed by hydrogen-bond mediated folding of the peptide backbone, and its changes have a significant impact on the bioavailability of proteins. As shown in fig. 4, further investigation of the extreme ultraviolet-CD spectrum showed conformational and structural change patterns of the pre-treated protein at different pH operating conditions. The results show that in the spectra of FIG. 4 (A-D), there are two distinct negative peaks at about 208 and 222nm, which are typically characteristic of an alpha-helical structure. And as shown in fig. 4 (a-d), the content of four monomers in the secondary conformation and structure of the BSA molecule was changed under different pH working conditions by correlation calculation. In detail, the content of α -helix, β -sheet, β -turn and disordered structures in the blank is 49.0%, 8.2%, 14.5% and 22.0%, respectively. The α -helix content of all samples pretreated under acidic conditions was reduced, wherein the α -helix content of the pretreated samples was reduced to 47.5% at ph=3, indicating that acidic pretreatment stimulated a decrease in the ordered helix of the peptide chains of the BSA molecules, resulting in an increase in protein wrinkles and disordered structures. Further, as shown in fig. 4C and 4C, investigation of the time economy of the acidic pretreatment (ph=3) showed that no significant difference in the secondary conformation and structure of BSA molecules occurred with the increase in the pretreatment time, and thus, 6h could be determined as the preferred point of the acid treatment.
In contrast, as shown in fig. 4B and 4B, the second structure of pretreated BSA at ph=12 showed a distinct structural transition from ordered to disordered, from folded to disordered. It is emphasized that the content of α -helix, β -sheet, β -turn and disordered structures is 26.3%, 29.5%, 18.9% and 32.2%, respectively. Alkaline pretreatment (ph=12) is more effective in destroying the secondary structure of proteins compared to acidic pretreatment of BSA, leading to a transition of proteins from ordered to disordered, especially β -sheet and disordered structures, which is positively correlated with degradation and utilization of proteins. Furthermore, the α -helix content in the AD methanogenesis process was reduced by 46.3% before pH adjustment to neutral, indicating that the hydrogen bonding network of the protein may be irreversibly broken under alkaline conditions at ph=12. Furthermore, as shown in fig. 4D and 4D, the time-economical investigation of alkaline pretreatment (ph=12) showed that the longer the time, the more pronounced the change in the secondary conformation and structure of the protein. Thus, the change in protein conformation and structure upon alkaline pretreatment (ph=12) is time dependent.
3. Fourier transform infrared spectrum of BSA after acid-base pretreatment
Typically, in FTIR spectra, the amide I and amide II bands are associated with the BSA secondary structure, which occur at 1600-1700cm -1 The absorption of the region associated with the c=o stretching vibration is noted as amide I, at about 1550cm -1 The absorption associated with N-H bending vibrations and C-N stretching vibrations, which is centered, is noted as amide II. As shown in fig. 5, the vibration frequency and vibration intensity of BSA were varied compared to the blank, whether pretreated with acidic or basic conditions. Protein molecules pretreated with acidic or basic conditions have a red shift in both the amide I and amide II bands with respect to changes in vibration frequency, indicating that hydrogen bonds in the molecule are being removedBreaking. In particular, the amide I band is in the spectral range of 1645cm -1 Side-to-side centered absorption may be due to exposure of the alpha-helical structure. While the shift of the exposed alpha-helical peak suggests that the BSA native structure is distorted due to the expansion of the helical structure, consistent with the observations of CD results. As for the vibration intensity, the alkaline pretreatment exhibited a stronger vibration amplitude, indicating that the degree of breakage of the hydrogen bond was greater than that of the acidic pretreatment during the alkaline pretreatment, which may explain that the methane yield performance of the alkaline pretreatment was superior. Thus, the greater sensitivity of the amide I band relative to the amide II band to BSA secondary structural changes suggests that c=o stretching vibration may be the primary trigger for the expansion of the α -helical structure, resulting in hydrogen bond cleavage.
Table 1 pH =3 and ph=12 fluorescence spectrum parameters at different pretreatment times
F * Representing the fluorescence intensity.
Claims (4)
1. A method for pretreatment of protein wastewater based on pH adjustment to increase the methanogenesis efficiency of AD, comprising the steps of:
step 1: microbial preparation
Centrifuging the anaerobic granular sludge at 12000rpm for 10min to remove soluble organic matters, and cleaning with distilled water for 2 times to obtain centrifugal granular sludge for later use;
step 2: pH pretreatment
The protein wastewater is subjected to pH adjustment treatment to change the pH value of the protein wastewater, and is rocked in an air bath cradle at room temperature for 6-24 hours to obtain protein wastewater after pH pretreatment;
step 3: anaerobic digestion
1) The protein wastewater after the pH pretreatment is readjusted to a pH neutral initial value to obtain neutral protein wastewater;
2) Then according to 150mL neutral protein waste water, 1mL microelement stock solution and 0.3g Na 2 HPO 4 、1 g NaHCO 3 Placing 15g centrifugal granular sludge in a reaction tank for mixing, and simultaneously, introducing helium to empty oxygen in the reaction tank so as to ensure an anaerobic environment in the reaction tank; the microelement stock solution is a Hunter microelement solution;
3) Then controlling the temperature in the reaction tank to be 35+/-1 ℃ and carrying out anaerobic digestion on a shaking table at a shaking speed of 120rpm, and collecting and producing methane;
the pH adjusting treatment in the step 2 specifically comprises the following steps: adopting acid pretreatment or alkaline pretreatment, wherein the pH of the protein wastewater is adjusted to 2-6 through 4M hydrochloric acid in the acid pretreatment; the pH of the protein wastewater is adjusted to 8-12 through 4M sodium hydroxide in the alkaline pretreatment;
the mixing mode in the step 3 specifically comprises the following steps: according to 150mL neutral protein wastewater, adding gelatin coated high carbon steel balls and 15g centrifugal granular sludge mixed slurry, wherein the gelatin coated high carbon steel balls account for 20-30% of the total volume of the neutral protein wastewater, and a mixed gelatin layer adopting the gelatin coated high carbon steel balls is added with 1mL trace element stock solution and 1g NaHCO 3 0.3g Na 2 HPO 4 。
2. The method for improving the methane production efficiency of AD based on the pretreatment of protein wastewater by adjusting the pH as claimed in claim 1, wherein the air bath shaker in the step 2 is specifically: shaking was performed at a shaking speed of 100rpm at room temperature of 25 ℃.
3. The method for improving AD methanogenesis efficiency based on pH adjustment of protein wastewater according to claim 1, wherein the mixed slurry is prepared by mixing gelatin coated high carbon steel balls with centrifugal granular sludge and stirring for 15min under the magnetic field strength of 0.1-0.2T before adding neutral protein wastewater.
4. The method for improving the methane production efficiency of AD based on pH adjustment pretreatment of protein wastewater as claimed in claim 1, wherein the preparation method of the gelatin coated high-carbon steel balls is specifically as follows:selecting high-carbon steel balls with particle size of 1+/-0.1 and cm, and storing microelement stock solution and NaHCO 3 Na (sodium carbonate) 2 HPO 4 Mixing with gelatin to obtain mixed gelatin, and coating the mixed gelatin on the surface of high carbon steel beads to make the thickness of the mixed gelatin coated on the high carbon steel be 0.6+/-0.05 cm.
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