CN113501644A - Preparation for improving organic solid waste anaerobic fermentation efficiency and preparation method and application thereof - Google Patents
Preparation for improving organic solid waste anaerobic fermentation efficiency and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation for improving anaerobic fermentation efficiency of organic solid waste and a preparation method and application thereof, belonging to the technical field of organic solid waste treatment. The preparation for improving the anaerobic fermentation efficiency of the organic solid waste comprises immobilized biological enzyme, co-metabolic nutrient substances and organic polymer. The method utilizes the composition and the structural characteristics of organic solid waste, improves the activity and the stability of enzyme in a form of fixing enzyme, converts macromolecules in sludge into small molecules, promotes the life activity of anaerobic microorganisms in sludge through co-metabolism nutrition, degrades organic matters which are difficult to decompose, and finally improves the stability of sludge communities and the stability of sludge of a reaction system through flocculation bridging of organic macromolecules, thereby realizing the aims of recycling and reducing organic solid waste.
Description
Technical Field
The invention belongs to the technical field of organic solid waste treatment, and particularly relates to a preparation for improving the anaerobic fermentation efficiency of organic solid waste and a preparation method and application thereof.
Background
In recent years, with the development of economy, the yield of organic solid wastes continues to increase. The organic solid waste components are relatively complex, comprise municipal sludge, industrial sludge, kitchen waste, straws and the like, and have resource properties and pollution properties. If the organic solid waste is properly treated, the waste is changed into valuable, otherwise, secondary pollution is caused.
The invention has application number 201010580486.2 and the name of the invention is: the invention discloses a Chinese patent for producing organic fertilizer and equipment by subcritical water treatment of urban and rural organic solid waste. However, the subcritical reaction condition is 180-230 ℃ and 1.55-3.0 MPa, the operation energy consumption is high, and in addition, toxic gas is easily generated in the subcritical hydrothermal process, so that secondary pollution is caused or tail gas treatment equipment needs to be equipped, and therefore, the large-scale application is difficult in the market.
The invention has application number 201811172817.1 and the name of the invention is: the invention discloses a method for improving the efficiency of high-solid anaerobic fermentation methane production of organic wastes, which is characterized in that the efficiency of high-solid anaerobic fermentation methane production of the organic wastes is improved by adding biochar, and the porous structure and the electrical conductivity of the biochar are beneficial to anaerobic acid production and the stability of methanogenic bacteria community is improved, so that the anaerobic fermentation efficiency is improved, but the biochar is large in dosage and the economic value needs to be improved.
The invention has application number 201410841735.7 and the name of the invention is: the invention discloses a method for producing short-chain volatile fatty acid by utilizing kitchen waste and a Chinese patent invention of the short-chain volatile fatty acid, which discloses a method for inoculating activated sludge into a kitchen waste fermentation system and utilizing a biosurfactant to improve the life activity of microorganisms, thereby producing the short-chain volatile fatty acid, realizing the reduction, recycling and harmless treatment of the kitchen waste, and having the advantages of low operation cost, high income, high yield of the short-chain volatile fatty acid and the like. But the method has a narrow adaptation range.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings of the prior art and provides a preparation for improving the organic solid waste anaerobic fermentation efficiency. The specific principle of the invention is that immobilized biological enzyme and co-metabolism nutrition are adopted to excite the rapid propagation of organic solid waste indigenous microorganisms, and the stability of anaerobic granular sludge community is improved through flocculation and bridging of organic macromolecules, thereby realizing the harmlessness, reclamation and reduction of organic solid waste.
The invention also aims to provide a preparation method of the preparation for improving the efficiency of the organic solid waste anaerobic fermentation.
The invention further aims to provide application of the preparation for improving the efficiency of the organic solid waste anaerobic fermentation.
The above object of the present invention is achieved by the following technical solutions:
a preparation for improving the anaerobic fermentation efficiency of organic solid wastes comprises immobilized biological enzymes, co-metabolic nutrients and organic polymers.
The co-metabolizing nutrient includes but is not limited to at least one of glucose, ethanol, sucrose and sodium acetate; more preferably at least one of glucose and sodium acetate.
The organic polymer includes but is not limited to at least one of Polyacrylamide (PAM), chitosan, cyclodextrin and amylopectin; preferably: at least one of Polyacrylamide (PAM) with a molecular weight of 800-2000 ten thousand and chitosan with a viscosity of 200-600 mPa.s; more preferably at least one of polyacrylamide having a molecular weight of 1400 ten thousand and chitosan having a viscosity of 400 mpa.s.
The mass ratio of the immobilized biological enzyme to the co-metabolic nutrient and the organic polymer is preferably 0.05-0.40: 0.5-1: 0.001.
The immobilized biological enzyme is prepared by the following preparation method:
s1, mixing Fe3O4@SiO2-NH2Dispersing in the solution 1, performing ultrasonic dispersion to obtain a dispersed mixture, adding glutaraldehyde, and washing to magnetically separate out solids;
s2, dissolving the solid by using the solution 2, adding the biological enzyme for reaction, washing and magnetically separating, and freeze-drying to obtain the immobilized biological enzyme.
In step S1, Fe3O4@SiO2-NH2The preparation method comprises the following steps:
1)Fe3O4preparation of NPs: FeCl3Dispersing in ethylene glycol, and ultrasonic dispersing to obtainAdding sodium citrate dihydrate and sodium acetate into brick red, stirring and mixing uniformly to brown, performing hydrothermal reaction, performing magnetic separation, rapidly cleaning with 0.1M dilute nitric acid of 1/10 magnetic separation to obtain solid, performing ultrasonic treatment, sequentially washing with ethanol and water, and freeze-drying the obtained solid to obtain powdered Fe3O4NPs；
2)Fe3O4@SiO2-NH2The preparation of (1): mixing Fe3O4Dispersing NPs into the mixed solution of ethanol and water, stirring uniformly in water bath, dripping ammonia water and TEOS into the mixed solution, continuously reacting, carrying out magnetic separation, and freeze-drying to obtain powdery Fe3O4@SiO2；
3)Fe3O4@SiO2-NH2The preparation of (1): to Fe3O4@SiO2Adding ethanol, ultrasonic treating, mixing in water bath, adding ammonia water and 3-aminopropyltriethoxysilane dropwise, reacting, washing to neutrality, and freeze drying to obtain Fe3O4@SiO2-NH2。
In particular, said Fe3O4@SiO2-NH2The preparation method comprises the following steps:
1)Fe3O4preparation of NPs: 1.3g of FeCl3Dispersing in 40.0mL of glycol, performing ultrasonic dispersion for 10-60 min to fully dissolve the Fe-B for 10h at 200 ℃, performing magnetic separation, adding 0.1M dilute nitric acid according to the volume ratio of 0.1M dilute nitric acid to 10:1 of magnetically separated solid, performing ultrasonic treatment for 10min, washing with ethanol and deionized water sequentially, dispersing in deionized water, freezing for 12h at-70 ℃, and performing freeze drying to obtain powdery Fe3O4NPs；
2)Fe3O4@SiO2-NH2The preparation of (1): 0.05g of Fe was taken3O4The NPs are dispersed into 100mL of mixed solution of ethanol and water (ethanol: water in volume ratio)1: 4), adding 1mL of 28% (v/v) ammonia water and 2.0mL of Tetraethoxysilane (TEOS) into a water bath at 40 ℃ while stirring at 300-600 r/min in sequence, continuously reacting for 6h, carrying out magnetic separation and cleaning, freezing for 12h at-70 ℃, and carrying out freeze drying to obtain powdery Fe3O4@SiO2；
3) 1g Fe was added to a round bottom flask3O4@SiO2And 60mL of absolute ethyl alcohol, performing ultrasonic treatment for 10-30 min, respectively adding 6.0mL of 28% (v/v) ammonia water and 4mL of 3-Aminopropyltriethoxysilane (APTES) at a dropping speed under stirring in a water bath at 50-90 ℃ at 300-600 r/min, continuously reacting for 8h, washing to be neutral, and performing freeze drying to obtain Fe3O4@SiO2-NH2。
Solution 1 described in step S1 is preferably phosphate buffered saline; more preferably: a phosphate buffer solution with a pH of 7.5-8.5; more preferably: phosphate buffer at pH 7.8.
Fe described in step S13O4@SiO2-NH2The mass-to-volume ratio of the solution to the solution 1 is 1: 50-150 in terms of g/mL; more preferably in terms of a mass-to-volume-in-mL ratio of 1: 90.
The conditions of the ultrasonic treatment described in step S1 are preferably: the time is 5-30 minutes, and the power is 100-300W; more preferably: time 10 minutes and power 200W.
The glutaraldehyde used in step S1 is preferably 50% (v/v) glutaraldehyde.
The solution 1 and the glutaraldehyde in the step S1 are preferably calculated according to the volume ratio of 7-11: 1; more preferably as 9: 1.
In the washing and magnetic separation of the solid in the step S1, the washing condition is preferably 25 ℃ and 200rpm shake washing for 2 h.
Solution 2 described in step S2 is preferably phosphate buffered saline; more preferably: a phosphate buffer solution with a pH of 4.5-6.5; more preferably: phosphate buffer at pH 5.2.
Fe described in step S23O4@SiO2-NH2The mass-to-volume ratio of the solution to the solution 2 is 1: 100-300 in g/mL; more preferably in terms of a mass-to-volume-in-mL ratio of 1: 200.
The biological enzyme in step S2 and Fe in step S13O4@SiO2-NH2Preferably, the mass ratio is 0.5-4: 1; more preferably, the mass ratio is 1.5-4: 1.
The biological enzyme described in step S2 preferably includes at least one of acid protease, pectinase, laccase, cellulase, lipase, amylase, lysozyme and dehydrogenase; more preferably at least three of acid protease, pectinase, laccase and cellulase.
The reaction conditions described in step S2 are: reacting at 2-8 ℃ and 50-300 rpm for 1-4 h; more preferably, the reaction is carried out at 4 ℃ and 200rpm for 2 hours.
The drying described in step S2 is preferably freeze drying.
The preparation method of the preparation for improving the organic solid waste anaerobic fermentation efficiency comprises the following steps: mixing immobilized biological enzyme, co-metabolism nutrient and organic polymer uniformly according to conventional method.
Specifically, the preparation method of the preparation for improving the organic solid waste anaerobic fermentation efficiency comprises the following steps:
(1) preparation of immobilized biological enzyme: mixing Fe3O4@SiO2-NH2Dispersing in the solution 1, performing ultrasonic dispersion to obtain a dispersed mixture, adding glutaraldehyde, and washing to magnetically separate out solids;
dissolving the solid with solution 2, adding biological enzyme for reaction, washing and magnetically separating, and freeze drying to obtain immobilized biological enzyme;
(2) and (2) uniformly mixing the immobilized biological enzyme obtained in the step (1) with co-metabolic nutrient substances and organic polymers to obtain the preparation for improving the anaerobic fermentation efficiency of organic solid wastes.
The preparation for improving the anaerobic fermentation efficiency of the organic solid waste is applied to the anaerobic fermentation of the organic solid waste.
A method for applying a preparation for improving the anaerobic fermentation efficiency of organic solid waste to the anaerobic fermentation production of volatile fatty acid of organic solid waste comprises the following steps: adding the preparation for improving the anaerobic fermentation efficiency of the organic solid waste into the organic solid waste for anaerobic fermentation, and supplementing the organic solid waste after the peak value of Volatile Fatty Acid (VFA) occurs.
The pH value of the organic solid waste is 3-11, and the water content is 70% -98%; more preferably, the pH is 7.2 and the water content is 75.30% to 92.3%.
The organic solid waste comprises but is not limited to at least one of kitchen waste, municipal sludge and industrial sludge; more preferably at least one of kitchen waste pulping liquid, municipal sludge and industrial sludge with the organic matter content of more than 30 percent.
The preparation for improving the anaerobic fermentation efficiency of the organic solid waste and the organic solid waste are preferably calculated according to the mass (mg) to volume (L) ratio of 10-500: 1; preferably in a mass (mg) to volume (L) ratio of 100: 1.
The anaerobic fermentation conditions are preferably as follows: introducing nitrogen for 10-180 s, at 20-300 rpm, at pH of 7.0-7.8, and culturing at constant temperature of 10-50 ℃; more preferably: introducing nitrogen for 30-180 s, 100-300 rpm, pH 7.0-7.8, and culturing at constant temperature of 35-50 ℃.
The time for reaching the peak value is preferably 3-11 days.
The amount of the supplemented organic solid waste is preferably calculated according to the hydraulic retention time of 5-20 d; more preferably calculated as the hydraulic retention time 10 d.
Compared with the prior art, the invention has the following advantages and effects:
(1) the method utilizes the composition and the structural characteristics of organic solid wastes, improves the activity and the stability of enzyme in a form of fixing enzyme, converts macromolecules in sludge into small molecules, promotes the life activity of anaerobic microorganisms in the sludge through co-metabolism nutrition, degrades organic matters which are difficult to decompose, and finally improves the stability of a sludge community and the stability of sludge of a reaction system through flocculation bridging of organic macromolecules, thereby realizing the aims of recycling and reducing the organic solid wastes.
(2) The preparation for improving the anaerobic fermentation efficiency of the organic solid waste has the advantages of simple synthesis process, low cost, convenient use and wide application range.
Drawings
FIG. 1 is a graph showing infrared spectra of each enzyme of example 1 before and after immobilization.
FIG. 2 is a zeta potential diagram of three immobilized enzymes of example 1; wherein, FIG. a) is a process chart of enzyme immobilization; panel b) is a zeta potential map before and after immobilization of the acid protease; panel c) is a zeta potential map before and after pectinase immobilization; panel d) is zeta potential map before and after laccase immobilization.
FIG. 3 is a graph showing the results of the change with time of VFA contained in each liter of the mixed liquid in example 2 and comparative examples 4 to 9.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
In the examples, Fe3O4@SiO2-NH2The preparation method comprises the following steps:
1)Fe3O4preparation of NPs: 1.3g of FeCl3Dispersing in 40.0mL of glycol, performing ultrasonic dispersion for 10-60 min to fully dissolve the Fe-B for 10h at 200 ℃, performing magnetic separation, adding 0.1M dilute nitric acid according to the volume ratio of 0.1M dilute nitric acid to 10:1 of magnetically separated solid, performing ultrasonic treatment for 10min, washing with ethanol and deionized water sequentially, dispersing in deionized water, freezing for 12h at-70 ℃, and performing freeze drying to obtain powdery Fe3O4NPs；
2)Fe3O4@SiO2-NH2The preparation of (1): 0.05g of Fe was taken3O4Dispersing NPs into 100mL of mixed solution of ethanol and water (the volume ratio of ethanol to water is 4:1), adding 1mL of 28% (v/v) ammonia water and 2.0mL of Tetraethoxysilane (TEOS) at the speed of dripping while stirring in water bath at 40 ℃ at 300-600 r/min, continuously reacting for 6h, carrying out magnetic separation and cleaning, freezing at-70 ℃ for 12h, and carrying out freeze drying to obtain powdery Fe3O4@SiO2；
3) 1g Fe was added to a round bottom flask3O4@SiO2And 60mL of absolute ethyl alcohol, carrying out ultrasonic treatment for 10-30 min, carrying out water bath at 50-90 ℃, stirring at 300-600 r/min,respectively adding 6.0mL of 28% (v/v) ammonia water and 4mL of 3-Aminopropyltriethoxysilane (APTES) at a dropping speed, continuously reacting for 8h, washing to neutrality, and freeze-drying to obtain Fe3O4@SiO2-NH2。
Example 1:
a preparation method of a preparation for improving the anaerobic fermentation efficiency of organic solid waste comprises the following steps:
(1) preparation of immobilized enzyme:
a1: preparation of immobilized acid protease: 0.1g of Fe having a particle size of about 500nm3O4@SiO2-NH2Dispersing in 9mL phosphate buffer solution (pH 7.8), and carrying out ultrasonic treatment for 10 minutes at the ultrasonic power of 200W to obtain a dispersed mixture; adding 1mL of 50% (v/v) glutaraldehyde solution into the dispersed mixture, washing for 2h at 25 ℃ and 200rpm with shaking, and magnetically separating out solids;
a2: and (2) re-dissolving the solid obtained by screening in the step A1 by using 20mL of phosphate buffer solution with the pH of 5.2, adding 0.05g of acid protease (50u/mg), reacting at 4 ℃ for 2h at 200rpm, washing for 3-5 times by using the phosphate buffer solution with the pH of 5.2, sucking the solid by using a magnet, and freeze-drying to obtain the immobilized acid protease (42.51 u/mg).
B1: preparation of immobilized pectinase: 0.1g of Fe having a particle size of about 500nm3O4@SiO2-NH2Dispersing in 9mL phosphate buffer solution (pH 7.8), and carrying out ultrasonic treatment for 10 minutes at an ultrasonic power of 200W to obtain a dispersed mixture; adding 1mL of 50% (v/v) glutaraldehyde solution into the dispersed mixture, washing for 2h at 25 ℃ and 200rpm with shaking, and magnetically separating out solids;
b2: and (3) redissolving the solid obtained by screening in the step B1 by using 20mL of phosphate buffer solution with the pH value of 5.2, adding 0.05g of pectinase (500u/mg), reacting at 4 ℃ for 2h at 200rpm, washing for 3-5 times by using the phosphate buffer solution with the pH value of 5.2, absorbing the solid by using a magnet, and freeze-drying to obtain the immobilized pectinase (42.51 u/mg).
C1: preparation of immobilized laccase: 0.1g of Fe having a particle size of about 500nm3O4@SiO2-NH2Dispersed in 9mL of phosphate buffer solutionCarrying out ultrasonic treatment in the liquid (the pH is 7.8) for 10 minutes at the ultrasonic power of 200W to obtain a dispersed mixture; adding 1mL of 50% (v/v) glutaraldehyde solution into the dispersed mixture, washing for 2h at 25 ℃ and 200rpm with shaking, and magnetically separating out solids;
c2: re-dissolving the solid obtained by screening in the step B1 with 20mL of phosphate buffer solution with the pH of 5.2, adding 0.05g of laccase (500u/mg), reacting at 4 ℃ and 200rpm for 2h, washing with phosphate buffer solution with the pH of 5.2 for 3-5 times, absorbing the solid with a magnet, and freeze-drying to obtain immobilized laccase (42.51 u/mg);
the infrared spectra of acid protease, pectase and laccase before and after immobilization are shown in FIG. 1.
As can be seen from FIG. 1, the immobilized enzyme was at 1230cm, compared to the free enzyme-1A new chemical bond is generated, which indicates that the free enzyme can be fixed on Fe through the form of covalent bond3O4@SiO2-NH2The above.
The process of immobilization of acid protease, pectinase and laccase is shown in a) of FIG. 2.
Acid protease, pectinase, laccase, immobilized acid protease, immobilized pectinase, immobilized laccase, and Fe3O4@SiO2-NH2The zeta potential of (a) is shown in Table 1 below and in FIGS. 2 b) to d):
table 1:
as can be seen from table 1 and fig. 2: the zeta potential of the immobilized acid protease, immobilized pectinase and immobilized laccase is improved after the enzyme is immobilized, and the free enzyme can also be immobilized on Fe in an electrostatic combination mode3O4@SiO2-NH2The above.
(2) And (2) uniformly mixing 0.05g of the immobilized acid protease, 0.05g of the immobilized pectinase and 0.001g of the immobilized laccase which are obtained in the step (1) with 1g of glucose and 0.001g of Polyacrylamide (PAM) with the molecular weight of 1400 ten thousand, so as to obtain the preparation for improving the anaerobic fermentation efficiency of the organic solid wastes.
A method for applying a preparation for improving the anaerobic fermentation efficiency of organic solid waste to the anaerobic fermentation production of volatile fatty acid of organic solid waste comprises the following steps:
taking 1L of sludge in a concentration tank of a Pouzhou sewage treatment plant in Foshan City, putting the sludge into a conical flask, adjusting the pH to 7.2 to obtain a mixed solution, wherein the water content of the sludge is 92.3 percent and the organic matter content (namely original VSS) of the sludge is 43.2 percent, and adding a preparation for improving the anaerobic fermentation efficiency of organic solid waste into the mixed solution according to the amount of 100 mg/L; and introducing nitrogen into the anaerobic fermentation tank for 30s, culturing at 100rpm and 35 ℃ in a dark constant temperature with the pH value of 7.0-7.8, and continuously measuring the VFA content. VFA appeared to peak at 68.43 + -1.29 mg/L at 3 rd, then organic solid waste was added at 0.1L/d (hydraulic retention time 10d) from 4 th, and VSS and VFA were continuously monitored for a total period of 30 days.
Comparative example 1:
the comparative example is basically the same as the example 1, except that the preparation for improving the organic solid waste anaerobic fermentation efficiency of the comparative example does not contain immobilized enzyme, and only contains glucose and polyacrylamide; the peak of VFA appeared to be 47.80 + -2.23 mg/L at 3 rd, then the organic solid waste was added at 0.1L/d (hydraulic retention time 10d) at 4 th, and VSS and VFA were continuously monitored.
Comparative example 2:
the comparative example is basically the same as the example 1, except that the preparation for improving the anaerobic fermentation efficiency of the organic solid waste of the comparative example only contains immobilized enzyme acid protease, immobilized pectinase and immobilized laccase, and does not contain glucose and polyacrylamide; at 5d, VFA peaked at 39.73 + -1.57 mg/L, and then at 6d organic solid waste was added at 0.1L/d (hydraulic retention time 10d) and VSS and VFA were continuously monitored.
Comparative example 3:
the comparative example is basically the same as the example 1, except that the comparative example does not add an agent for improving the anaerobic fermentation efficiency of the organic solid waste into the sludge of the thickening tank; at 15 th day, the peak of VFA appeared at 4.09. + -. 0.45mg/L, and then at 16 th day, the organic solid waste was started to be added at 0.1L/d (hydraulic retention time 10d), and VSS and VFA were continuously measured.
Example 2:
this example is substantially the same as example 1, except that the enzymes selected in step (1) of example 2 are 0.05g acid protease (50u/mg), 0.05g pectinase (500u/mg), 0.05g cellulase (500u/mg) and 0.05g laccase (500u/mg), respectively, to finally prepare immobilized acid protease (48.19u/mg), immobilized pectinase (459.23u/mg), immobilized cellulase (468.39u/mg) and immobilized laccase (467.77 u/mg);
wherein, the preparation method of the immobilized acid protease (48.19u/mg), the immobilized pectinase (459.23u/mg) and the immobilized laccase (467.77u/mg) is the same as that of the example 1;
the preparation method of the immobilized cellulase comprises the following steps: d1: preparation of immobilized cellulase (468.39 u/mg): 0.1g of Fe having a particle size of about 500nm3O4@SiO2-NH2Dispersing in 9mL phosphate buffer solution (pH is 7.8), and carrying out ultrasonic treatment for 10 minutes at an ultrasonic power of 200W to obtain a dispersed mixture; adding 1mL of 50% (v/v) glutaraldehyde solution into the dispersed mixture, washing for 2h at 25 ℃ and 200rpm with shaking, and magnetically separating out solids;
d2: re-dissolving the solid obtained by screening in the step B1 with 20mL of phosphate buffer solution with the pH value of 5.2, then adding 0.05g of cellulase (468.39u/mg), reacting at 4 ℃ and 200rpm for 2h, washing with 0.5mol/L phosphate buffer solution with the pH value of 5.2 for 3-5 times, then sucking the solid with a magnet, and freeze-drying to obtain immobilized cellulase (468.39 u/mg);
in the step (2), 0.1g of each of immobilized acid protease (48.19u/mg), immobilized pectinase (459.23u/mg), immobilized cellulase (468.39u/mg) and immobilized laccase (467.77u/mg) and 0.5g of each of sodium acetate and 0.001g of chitosan (purchased from Shanghai Michelin Biochemical technology Co., Ltd.; the same below) with the viscosity of 400mPa.s are uniformly mixed to obtain the preparation for improving the anaerobic fermentation efficiency of organic solid wastes.
A method for applying a preparation for improving the anaerobic fermentation efficiency of organic solid waste to the anaerobic fermentation production of volatile fatty acid of organic solid waste comprises the following steps:
uniformly mixing 950mL of kitchen waste size mixing liquid of a certain factory and 50mL of municipal sludge, putting the mixture into a conical flask, adjusting the pH value to 7.2 to obtain a mixed liquid, wherein the water content of the mixed liquid is 75.30%, the granularity of the mixed liquid is less than 2mm, and the organic matter content of the mixed liquid is 78.22%, and adding a preparation for improving the anaerobic fermentation efficiency of organic solid waste into the mixed liquid according to the amount of 100 mg/L; then introducing nitrogen for 30s, culturing at 100rpm, 35 ℃ and constant temperature in a dark place with pH of 7.0-7.8, and continuously measuring the VFA content. After 11 days VFA appeared to have a peak value of 1.37 +/-0.01 g/L, the organic solid waste was added at 0.1L/d (hydraulic retention time of 10d), and VSS and VFA were continuously detected for a total period of 30 days.
The basic properties of the kitchen waste slurry and municipal sludge before and after mixing are shown in table 2.
Table 2: basic properties of kitchen waste size and municipal sludge before and after mixing
Comparative example 4
This comparative example is substantially the same as example 2 except that no agent for improving the efficiency of the organic solid waste anaerobic fermentation is added in this comparative example 4; at 23d, VFA peaked at 0.93. + -. 0.02g/L, and the other operations were the same as in example 2.
Comparative example 5
This comparative example is substantially the same as example 2 except that the preparation for improving the efficiency of organic solid waste anaerobic fermentation of this comparative example consists of 0.5g of sodium acetate and 0.001g of chitosan having a viscosity of 400 mpa.s; at 23d, VFA peaked at 1.12. + -. 0.06g/L, and the other operations were the same as in example 2.
Comparative example 6
This comparative example is substantially the same as example 2 except that the preparation for improving the efficiency of anaerobic fermentation of organic solid wastes of this comparative example consists of 0.4g of immobilized acidic protease, 0.5g of sodium acetate and 0.001g of chitosan (available from Shanghai Merlan Biotech Co., Ltd.) having a viscosity of 400 mPa.s; the 11d VFA showed a peak of 1.03. + -. 0.02g/L, and the other operations were the same as in example 2.
Comparative example 7
This comparative example is substantially the same as example 2, except that the preparation for improving the efficiency of organic solid waste anaerobic fermentation of this comparative example consists of 0.4g of immobilized pectinase, 0.5g of sodium acetate and 0.001g of chitosan having a viscosity of 400 mpa.s; the 15d VFA showed a peak of 1.13. + -. 0.04g/L, and the other operations were the same as in example 2.
Comparative example 8
This comparative example is substantially the same as example 2 except that the preparation for improving the efficiency of organic solid waste anaerobic fermentation of this comparative example consists of 0.4g of immobilized cellulase, 0.5g of sodium acetate and 0.001g of chitosan having a viscosity of 400 mpa.s; the 15 th VFA showed 1.17. + -. 0.23g/L peak, and the other operations were the same as in example 2.
Comparative example 9
The comparative example is basically the same as example 2, except that the preparation for improving the organic solid waste anaerobic fermentation efficiency of the comparative example consists of 0.4g of immobilized laccase, 0.5g of sodium acetate and 0.001g of chitosan with the viscosity of 400 mPa.s; the peak value of VFA at 13d was 0.89. + -. 0.03g/L, and the operation was otherwise the same as in example 2.
After day 30, the results of the changes over time of VFA contained in each liter of the mixed solution of example 2 and comparative examples 4 to 9 are shown in FIG. 3.
As can be seen from fig. 3, example 2 added an agent that increased the efficiency of the anaerobic fermentation of organic solid waste, the speed and yield of VFA production by the anaerobic fermentation system was significantly increased compared to comparative examples 4-9.
The embodiments of the present invention are not limited to the above-described embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and they are included in the scope of the present invention.
Claims (10)
1. A preparation for improving the anaerobic fermentation efficiency of organic solid wastes is characterized by comprising immobilized biological enzymes, co-metabolic nutrients and organic polymers.
2. The formulation of claim 1, wherein said co-metabolizing nutrients include, but are not limited to, at least one of glucose, ethanol, sucrose, and sodium acetate;
the organic polymer includes but is not limited to at least one of polyacrylamide, chitosan, cyclodextrin and amylopectin;
the mass ratio of the immobilized biological enzyme to the co-metabolic nutrient and the organic polymer is 0.05-0.40: 0.5-1: 0.001.
3. The formulation of claim 2, wherein the co-metabolizing nutrient is at least one of glucose and sodium acetate;
the organic polymer is at least one of polyacrylamide with the molecular weight of 800-2000 ten thousand and chitosan with the viscosity of 200-600 mPa.s.
4. The preparation of claim 1, wherein the immobilized biological enzyme is prepared by the following preparation method:
s1, mixing Fe3O4@SiO2-NH2Dispersing in the solution 1, performing ultrasonic dispersion to obtain a dispersed mixture, adding glutaraldehyde, and washing to magnetically separate out solids;
s2, dissolving the solid by using the solution 2, adding the biological enzyme for reaction, washing and magnetically separating, and freeze-drying to obtain the immobilized biological enzyme.
5. The formulation of claim 4,
in step S1, Fe3O4@SiO2-NH2The preparation method comprises the following steps:
1)Fe3O4preparation of NPs: FeCl3Dispersing in ethylene glycol, ultrasonically dispersing until the color is brick red, adding sodium citrate dihydrate and sodium acetate, stirring, mixing to brown, performing hydrothermal reaction, magnetically separating, rapidly cleaning with 0.1M dilute nitric acid (1/10) in volume of solid obtained by magnetic separation, ultrasonically treating, sequentially washing with ethanol and water, and freeze drying to obtain powdered Fe3O4 NPs；
2)Fe3O4@SiO2-NH2The preparation of (1): mixing Fe3O4Dispersing NPs into the mixed solution of ethanol and water, stirring in water bath, adding dropwise ammonia water and TEOS, reacting, magnetically separating, and freeze drying to obtain powdered Fe3O4@SiO2；
3)Fe3O4@SiO2-NH2The preparation of (1): to Fe3O4@SiO2Adding ethanol, performing ultrasonic treatment, mixing in water bath, adding ammonia water and 3-aminopropyltriethoxysilane dropwise, reacting, washing to neutrality, and freeze drying to obtain Fe3O4@SiO2-NH2；
Fe described in step S13O4@SiO2-NH2The mass-to-volume ratio of the solution to the solution 1 is 1: 50-150 in terms of g/mL;
solution 1 in step S1 is phosphate buffer;
fe described in step S23O4@SiO2-NH2The mass-to-volume ratio of the solution to the solution 2 is 1: 100-300 in g/mL;
solution 2 in step S2 is phosphate buffer;
the biological enzyme in the step S2 comprises at least one of acid protease, pectinase, laccase, cellulase, lipase, amylase, lysozyme and dehydrogenase;
the biological enzyme in step S2 and the Fe in step (1)3O4@SiO2-NH2According to the mass ratio of 0.5-4: 1;
and calculating the solution 1 and the glutaraldehyde in the step S1 according to the volume ratio of 7-11: 1.
6. The formulation of claim 5,
the biological enzymes in the step S2 are at least three of acid protease, pectinase, laccase and cellulase;
the biological enzyme in step S2 and Fe in step S13O4@SiO2-NH2According to the mass ratio of 1.5-4Calculating;
the solution 1 in the step S1 is a phosphate buffer solution with the pH value of 7.5-8.5;
the ultrasonic processing conditions described in step S1 are: the time is 5-30 minutes, and the power is 100-300W;
the solution 2 in the step S2 is a phosphate buffer solution with the pH value of 4.5-6.5;
the reaction conditions described in step S2 are: reacting at 2-8 ℃ and 50-300 rpm for 1-4 h;
the drying described in step S2 is freeze-drying.
7. The preparation method of the preparation for improving the anaerobic fermentation efficiency of the organic solid waste according to any one of claims 1 to 6, characterized by comprising the steps of uniformly mixing the immobilized biological enzyme, the co-metabolic nutrient and the organic polymer according to a conventional method;
specifically, the method comprises the following steps:
(1) preparation of immobilized biological enzyme: mixing Fe3O4@SiO2-NH2Dispersing in the solution 1, performing ultrasonic dispersion to obtain a dispersed mixture, adding glutaraldehyde, and washing to magnetically separate out solids;
dissolving the solid with solution 2, adding biological enzyme for reaction, washing and magnetically separating, and freeze drying to obtain immobilized biological enzyme;
(2) and (2) uniformly mixing the immobilized biological enzyme obtained in the step (1) with co-metabolic nutrient substances and organic polymers to obtain the preparation for improving the anaerobic fermentation efficiency of organic solid wastes.
8. The application of the preparation for improving the anaerobic fermentation efficiency of the organic solid waste in the claims 1 to 6 in the anaerobic fermentation of the organic solid waste.
9. A method for producing volatile fatty acid by applying the preparation for improving the anaerobic fermentation efficiency of organic solid waste according to any one of claims 1 to 6 to the anaerobic fermentation of organic solid waste is characterized by comprising the following steps: adding the preparation for improving the anaerobic fermentation efficiency of the organic solid waste into the organic solid waste for anaerobic fermentation, and supplementing the organic solid waste after the peak value of the volatile fatty acid occurs.
10. The method of claim 9,
the pH value of the organic solid waste is 3-11, and the water content is 70% -98%;
the organic solid waste comprises but is not limited to at least one of kitchen waste, municipal sludge and industrial sludge;
the preparation for improving the anaerobic fermentation efficiency of the organic solid waste is calculated according to the mass mg volume L ratio of 10-500: 1 to the organic solid waste;
the anaerobic fermentation conditions are as follows: introducing nitrogen for 10-180 s at 20-300 rpm, pH of 7.0-7.8, and culturing at constant temperature of 10-50 ℃;
the time for reaching the peak value is 3-11 days;
and the amount of the supplemented organic solid waste is calculated according to the hydraulic retention time of 5-20 d.
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