CN109626375B - Manganese-doped magnetic carbon, preparation thereof and application thereof in hydrogen production by dark fermentation - Google Patents
Manganese-doped magnetic carbon, preparation thereof and application thereof in hydrogen production by dark fermentation Download PDFInfo
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Abstract
The invention relates to manganese-doped magnetic carbon, a preparation method thereof and application thereof in hydrogen production by dark fermentation. The preparation material takes ferric salt and manganese salt as raw materials, the reaction is carried out under the conditions of alkalinity and heating, substances generated by the reaction are uniformly loaded on the surface and in the pores of the carbon material, and the manganese-doped magnetic carbon is obtained by drying. The prepared manganese-doped magnetic carbon contains MnFe2O4、Fe2O3、MnCO3Etc. and has magnetic properties. Manganese-doped magnetic carbon is applied to the process of preparing hydrogen by dark fermentation, and the carbon can release trace elements such as iron and manganese in a liquid phase and can promote the activity of microorganisms; the carbon material can enrich microorganisms and form a stable biological film as a carrier, and provides a good environment for the growth and the propagation of the microorganisms; in addition, the manganese-doped magnetic carbon has unique physicochemical properties, and can be effectively separated from sludge by utilizing the magnetism of the manganese-doped magnetic carbon, so that the recycling of carbon materials and the improvement of the hydrogen production capability through fermentation are realized.
Description
Technical Field
The invention relates to the field of composite material synthesis and clean energy production, and particularly relates to manganese-doped magnetic carbon, and preparation and application thereof in a dark fermentation hydrogen production process.
Background
The ever-increasing demand for energy and the ever-decreasing supply of fossil energy forces mankind to face a range of energy crisis. Meanwhile, the ecological environment is destroyed due to the increase of the amount of pollutants such as solid waste, kitchen waste, livestock and poultry manure, agricultural solid waste and organic wastewater, and the human health is finally affected. In order to solve the series of problems, a novel technology is required to be developed to combine the energy shortage with the environmental pollution, so that the pollutants are degraded and consumed, and meanwhile, energy is provided for the production and the life of human beings. The hydrogen production process by dark fermentation is a low-energy consumption and environment-friendly technology, can combine energy regeneration and environmental remediation into a whole, and converts organic pollutants (such as kitchen waste, fruit and vegetable waste, livestock and poultry manure, agricultural straws, organic wastewater and the like) in the environment into renewable energy by degradation.
Hydrogen (H)2) Is considered to be an alternative energy source of ideal fossil fuel without pollution and regeneration. It contains 2.6 times the energy of methane combustion. Due to H2Combustion produces only water and can release a large amount of energy, making it an environmentally friendly energy source. The prior hydrogen production technology mainly comprises water electrolysis, light fermentation and dark fermentation hydrogen production methods. The hydrogen production technology by dark fermentation has the advantages of low energy consumption, simple and convenient operation, low cost and the like, and is the research object of multiple scholars in the literature, but the H is produced by the dark fermentation2The phenomena of organic acid accumulation and ammonia nitrogen inhibition are easy to occur in the system, which leads to H2The yield and the productivity are low, so that the industrial popularization and the application are difficult. The method for optimizing process design and key parameters can be to improve fermentation microenvironment to increase anaerobic microorganism activity and H2And (4) yield. In the biogas preparation process, carriers such as active zeolite, carbon materials, polyvinyl alcohol, glass and the like are added, so that the metabolism of anaerobic microorganisms can be effectively promoted. In the dark fermentation process, microorganisms can be enriched and fixed through the carrier to form a biological membrane, so that the loss of the microorganisms is reduced, and the resistance of the microorganisms to the change of the external environment is enhanced. In recent years, many carbon materials have been used as additives in the process of producing hydrogen by dark fermentation. The activated carbon is a very efficient amorphous carbon material and can provide a fixed residence for the growth and the propagation of microorganisms. The microbial flora can realize high-efficiency enrichment on the surface of the activated carbon, so that the activated carbon can absorb nutrient substances more fully, and organic substances are efficiently converted into H2. In addition, the conductivity of the activated carbon can obviously improve the direct electron transfer rate of microbial flora. The addition of activated carbon in the anaerobic reactor can promote the direct electron transfer rate of M.barkeri and G.metallareducens and improve the substrate metabolism efficiency. The highest H can be obtained when the ratio of the sludge to the active carbon is 1:22Yield and H yield2Rate, i.e. from 0.86mol H2The concentration of the substrate (glucose and xylose mixture) and 0.5 mmol/(g.h) is increased to 1.77mol H2Permol substrate and 2 mmol/(g.h) (International Journal of Hydrogen Energy, 2016, 41 (46): 21617-.
In addition, trace elements such as iron (Fe), manganese (Mn), cobalt (Co), nickel (Ni) and molybdenum (Mo) can activate enzyme catalysis in biochemical reaction, promote cell synthesis and improve bacterial activity. Iron is an important trace element, is a main component for forming iron-sulfur clusters in ferredoxin, and can be used for intracellular oxidation-reduction reaction of microorganisms. In addition, iron is involved in the synthesis of oxidases and cytochromes. In recent years, iron of different valence states and forms has been used as an additive in biological hydrogen production processes. Some researches prove that Fe with proper concentration is added into a system for producing hydrogen by dark fermentation3O4，Fe2O3And Fe2+Etc. can promote the activity of the iron-based hydrogenase. There is a document (International Journal of Hydrogen Energy, 2015, 40 (36): 12201-12208) showing that Fe is added in appropriate concentrations during dark fermentation0Can be combined with H2The yield is improved by 38.2 percent, and when Fe is added at the same time0And activated carbon, H can be2The yield is improved by 50.2%. In addition, the trace element manganese (Mn) is also a major additive to promote microbial growth. Studies (Journal of Biological Chemistry, 2004, 279(30), 31854-62) found phosphodiesterase activity in methanococcus jannaschii on Mn2+Has absolute requirements and can be in Mn2+And Ni2+In the presence of a protein containing a binuclear metal center. In dark fermentation, manganese is positively correlated with the relative abundance of other trace elements such as cobalt, molybdenum, nickel and tungsten with mcrA transcription in methanoscina sp.
The magnetic separation technology is a modern separation technology with high speed and high efficiency, and is widely applied to research directions of analytical chemistry, biochemistry, mining industry and the like. At present, the application of magnetic separation technology in environmental pollution treatment draws extensive attention, and researchers utilize Fe2O3And Fe3O4The particles are used as raw materials to synthesize the magnetic carbon material, are applied to removing dye in wastewater, can adsorb pollutants in water by utilizing the high adsorption performance of carbon, and can quickly separate the materials from the waterAnd (4) separation and recycling are realized. However, the application of magnetic separation technology in the process of biological hydrogen production has not been reported.
In patent application CN107227318A (application No. 201710622727.7), chloroform is used as an additive to achieve the purpose of improving the performance of hydrogen production by dark fermentation, and the method provided by the application can not realize the purposes of harmlessness and reclamation of kitchen waste, and can also improve the yield of hydrogen. However, chloroform is easily decomposed by light and generates harmful gas, which is harmful to human health.
In patent application CN104726501A (application No. 201510145589.9), calcium carbonate is used as an additive to improve the fermentation effect of bagasse, and although a better gas production effect is achieved, calcium carbonate is finally precipitated in the system, which results in an increase in sludge amount and thus does not enable sludge reduction treatment.
However, the additives for promoting hydrogen production by fermentation reported in the above documents have the disadvantages of complicated production process, high energy consumption or pollution generation, and the like, and limit the application of the additives in the field of large-scale hydrogen production by fermentation. The literature that manganese-doped magnetic carbon is used as a promoter for biological hydrogen production to improve the hydrogen production performance is not reported yet. Therefore, the object of this patent application is to invent the preparation of manganese-doped magnetic carbon and its application in the field of biological hydrogen production to obtain the highest H2Yield and fermentation efficiency.
Disclosure of Invention
The invention provides a preparation method of manganese-doped magnetic carbon, which is applied to a fermentation hydrogen production system to increase H2Yield and rate. The manganese-doped magnetic carbon takes manganese salt, ferric salt and active carbon as raw materials, and is reacted by adopting an oil bath heating mode to generate a magnetic carbon material containing Mn, Fe and other trace elements, wherein the material contains MnFe2O4、Fe2O3、MnCO3And the like, which can provide necessary trace elements for the metabolism of microorganisms in a fermentation system, promote the activity of hydrogenase, accelerate the growth rate of the trace elements and promote the enrichment of the microorganisms on the surface and in gaps of the surface so as to form a stable biological film, enhance the impact resistance of the microorganisms to the change of the external environment and improve the nutrient contents of the microorganismsUptake and metabolic rate thereof, obtaining maximum fermentation yield H2Capability. The manganese-doped magnetic carbon also has magnetism, is convenient to be quickly separated from sludge after the fermentation hydrogen production reaction is finished, and realizes the repeated use of carbon materials and sludge reduction treatment.
The manganese-doped magnetic carbon is characterized by mainly comprising active carbon and MnFe2O4、Fe2O3And MnCO3，MnFe2O4、Fe2O3And MnCO3Uniformly attached on the surface and in the pore diameter of the active carbon.
Elemental analysis of the manganese-doped magnetic carbon shows that the atomic percentages of C, O, Fe and Mn are 79-80%, 18-19%, 1-2% and 0.5-1%, respectively. Preferably, elemental analysis of manganese-doped magnetic carbon showed that C, O, Fe and Mn were 79.44%, 18.51%, 1.4% and 0.65% atomic percent, respectively.
Preferably, the manganese-doped magnetic carbon is characterized in that an X-ray diffraction pattern shows that characteristic peaks appear at 29.68 degrees, 34.91 degrees, 52.71 degrees and 56.12 degrees, and MnFe2O4Corresponding; characteristic peaks and Fe appear at 29.96 degrees, 32.80 degrees, 60.895 degrees and 67.72 degrees2O3Corresponding; characteristic peaks appear at 24.27 degrees, 31.38 degrees and 51.68 degrees, which indicates that the material contains trace MnCO3(ii) a When the 2 theta is 24-28 degrees, a peak appears, and the representative material contains activated carbon.
Preferably, the manganese-doped magnetic carbon is obtained by performing oil bath heating reflux reaction on manganese salt and ferric salt under an alkaline condition and drying.
The invention adopts the following technical scheme to prepare the manganese-doped magnetic carbon:
wherein, manganese ions and iron ions are subjected to oil bath heating reflux reaction in a reactor under the alkaline condition and rapidly react at a certain temperature to generate MnFe2O4(ii) a The residual iron ions in the solution react with hydroxide ions to generate ferric hydroxide, and the ferric hydroxide dehydrates under the heating condition to form Fe2O3(ii) a The residual manganese ions in the solution react with CO in the air under the alkaline condition2Reacting to generate trace MnCO3. The heating process lasts for a certain time, and MnFe is obtained after the reaction is completed2O4、Fe2O3And trace MnCO3Uniformly attaching the manganese-doped magnetic carbon on the surface and in the pore diameter of the active carbon, and drying at a certain temperature for a certain time to obtain the manganese-doped magnetic carbon.
The manganese ions and the iron ions take manganese salt and iron salt as raw materials. The manganese salt is one or more of manganese chloride, manganese sulfate, manganese nitrate or manganese phosphate; the ferric salt is one or more of ferric chloride, ferric sulfate, ferric nitrate or ferric acetate.
The alkaline condition is obtained by adjusting the pH value of NaOH solution to 10-12.
The oil bath is heated to a certain temperature, and the reflux reaction temperature is 100-130 ℃.
The oil bath is continuously heated and refluxed for 2-4 h.
Preferably, the molar ratio of manganese to iron to carbon is 1:2: 50-150. 3.75-37.5 g/L; the concentration of the ferric salt is 10.5-102 g/L; the concentration of the activated carbon is 45-450 g/L; the concentration of the NaOH solution is 20-129 g/L.
The certain temperature and time are 60-85 ℃ of drying temperature and 10-20 h of drying time.
The invention also provides a preparation method of the manganese-doped magnetic carbon, which comprises the following steps:
(1) manganese chloride, ferric chloride and active carbon are used as raw materials to prepare a ferro-manganese-carbon mixed solution;
(2) heating the mixed solution obtained in the step (1) in an oil bath to boiling, quickly introducing a NaOH solution into the boiling mixed solution, and uniformly stirring;
(3) boiling and refluxing at a certain temperature for reaction, pouring the reaction product into a beaker for cooling after the reaction is completed;
(4) and drying the mixed solution obtained in the step at a certain temperature to obtain the manganese-doped magnetic carbon.
Preferably, the preparation method of the manganese-doped magnetic carbon is characterized by comprising the following steps: the preparation method of the iron-manganese-carbon mixed solution comprises the following steps:
weighing 1-3 g of MnCl2·4H2O and 2.6-7.8 g FeCl3·6H2O particlesDissolving the mixture in 100-200 ml of deionized water, adding 12-36.4 g of activated carbon, and stirring for 1-2 hours to fully mix the mixture uniformly to obtain a ferro-manganese-carbon mixed solution. At this time, MnCl2The concentration of the solution is 5-30 g/L; FeCl3The concentration is 13-78 g/L; the concentration of the activated carbon is 60-364 g/L.
Preferably, the preparation method of the manganese-doped magnetic carbon is characterized by comprising the following steps: the oil bath method in step (2) is as follows:
the iron-manganese-carbon solution is carried out in a reactor, and the reactor is connected with a condensation reflux pipe. After the solution is boiled, the NaOH solution is quickly poured into the solution and stirred and mixed evenly.
Preferably, the preparation method of the manganese-doped magnetic carbon is characterized by comprising the following steps: the preparation method of the NaOH solution in the step (2) is as follows:
weighing 1.72-2.24 g of NaOH particles, and dissolving the NaOH particles in deionized water to obtain an alkali solution with the pH value of 10-12 d, wherein the concentration of NaOH is 34.4-129 g/L.
Preferably, the preparation method of the manganese-doped magnetic carbon is characterized by comprising the following steps: and (3) keeping the boiling reaction time for 1-2 h.
Preferably, the preparation method of the manganese-doped magnetic carbon is characterized by comprising the following steps: and (4) drying at the temperature of 60-85 ℃ for 10-20 h.
The invention also aims to provide application of the manganese-doped magnetic carbon, and the manganese-doped magnetic carbon is utilized to promote the hydrogen production performance by dark fermentation.
The application applies manganese-doped magnetic carbon to the process of producing hydrogen by dark fermentation, can make up the defects of low microbial quantity and enrichment capacity, insufficient trace elements, poor enzyme activity and the like in the fermentation process, and improves the hydrogen yield of a dark fermentation system by enriching anaerobic fermentation bacteria, promoting the formation of a biological membrane, providing necessary elements and good places for the growth and the propagation of microorganisms and the like. In addition, the manganese-doped magnetic carbon has magnetism, and can be efficiently separated from sludge, so that the reduction treatment of the sludge and the recycling of carbon materials are realized.
Drawings
FIG. 1X-ray diffraction pattern of manganese-doped magnetic carbon.
FIG. 2 is an analysis spectrum of manganese-doped magnetic carbon element.
FIG. 3 shows that the medium-temperature fermentation of manganese-doped magnetic carbon is added to promote the hydrogen production rate of glucose dark fermentation.
FIG. 4 shows that the hydrogen production rate of glucose dark fermentation is promoted by adding manganese-doped magnetic carbon for high-temperature fermentation.
Detailed Description
The following examples are further illustrative of the present invention, but the present invention is not limited thereto.
The preparation method of the manganese-doped magnetic carbon comprises the following specific steps:
A. 1-3 g of MnCl2·4H2O and 2.6-7.8 g FeCl3·6H2Dissolving O particles in 100-200 ml of deionized water, adding 12-36.4 g of activated carbon, and stirring for 1-2 hours to fully mix the mixture uniformly to obtain the iron-manganese-carbon mixed solution. At this time, MnCl2The concentration of the solution is 5-30 g/L; FeCl3The concentration is 13-78 g/L; the concentration of the activated carbon is 60-364 g/L; weighing 1.72-2.24 g of NaOH particles, and dissolving the NaOH particles in deionized water to obtain an alkali liquor with the pH of 10-12, wherein the concentration of NaOH is 34.4-129 g/L;
B. the mixed liquid is subjected to oil bath heating reflux reaction in a reactor, and the reactor is connected with a condensation reflux pipe. After the mixed solution is boiled, 50ml of 50g/L NaOH solution is quickly poured into the mixed solution, and the mixed solution is stirred and uniformly mixed;
C. boiling the mixed solution at 100-130 ℃, performing reflux reaction for 2-4 h, pouring the mixed solution into a beaker after the reaction is completed, and cooling;
D. and drying the mixed solution obtained in the step at the temperature of 60-85 ℃ to obtain the manganese-doped magnetic carbon.
The experiment for the influence of manganese-doped magnetic carbon on the performance of dark fermentation hydrogen production comprises the following specific steps:
A. taking dewatered sludge of an urban sewage treatment plant, and carrying out anaerobic standing for 15-35 d at room temperature or medium temperature (33-38 ℃) or high temperature (50-55 ℃) respectively to screen and enrich anaerobic fermentation bacteria;
B. carrying out heat treatment on the sludge subjected to enrichment at 85-100 ℃ for 30-60 min, cooling to a proper temperature (33-38 ℃ or 50-55 ℃) for producing hydrogen through dark fermentation, and then carrying out anaerobic acclimation and enrichment for 24-36 h (or until the system does not produce hydrogen) under the conditions that the glucose concentration is 0.5-2 g/L, the medium temperature (33-38 ℃) or the high temperature (50-55 ℃), so as to obtain an inoculum for producing hydrogen through dark fermentation;
C. respectively pouring five parts of 2.5-7.5 g of glucose, 0.05-0.15 g of peptone and 100-200 ml of hydrogen-producing inoculum into a fermentation reactor, and numbering 1-5;
D. weighing 100 mg, 200 mg, 300 mg and 400mg of manganese-doped magnetic carbon, and sequentially adding the manganese-doped magnetic carbon into a No. 2-5 reactor. Diluting all reactors to a constant volume of 500ml by using deionized water, wherein the concentration of glucose in the reactor is 5-15 g/L, the concentration of peptone is 0.1-0.3 g/L, the proportion of hydrogen production inoculum to the total fermentation volume (namely inoculum size) is 20-40%, and the concentration of manganese-doped magnetic carbon is 0-800 mg/L;
E. sealing the fermentation reactors with rubber plugs respectively, and connecting the fermentation reactors with a gas collecting device; sealing the reactor and carrying out anaerobic treatment; and (3) adjusting the temperature of a water bath temperature control system, wherein the fermentation temperature is 33-38 ℃ or 50-55 ℃, the fermentation time is 30-48 h (or until gas generation is stopped), and collecting the gas by adopting an alkali discharge (8-12% NaOH) method.
A method for improving the dark fermentation performance by using manganese-doped magnetic carbon is characterized in that the manganese-doped magnetic carbon is added into an anaerobic fermentation reactor to achieve the purposes of improving the hydrogen yield and the hydrogen production rate.
The fermentation substrate of the anaerobic fermentation reactor consists of a carbon source, a nitrogen source, an inoculum and manganese-doped magnetic carbon.
The method for improving the performance of dark fermentation hydrogen production by using manganese-doped magnetic carbon is characterized by comprising the following steps of:
(1) taking dewatered sludge of an urban sewage treatment plant, and carrying out anaerobic culture at a certain temperature to screen and enrich anaerobic fermentation bacteria. The dewatered sludge is obtained by standing the sludge for 15-35 d at room temperature, medium temperature (33-38 ℃) or high temperature (50-55 ℃) respectively. The dewatered sludge is sourced from a sludge dewatering room of an urban sewage treatment plant, the water content is 78-92%, and the organic matter content in the sludge is 30-75%; the proportion of the hydrogen-producing inoculum to the total volume of the fermentation is 20-40%;
(2) and (2) carrying out heat treatment on the sludge obtained in the step (1) for 30-90 min, inhibiting the activity of hydrogen-consuming bacteria and methanogens, cooling, and adding a small amount of nutrients to acclimate the sludge at a certain temperature to obtain a hydrogen-producing inoculum. Carrying out heat treatment on the enriched sludge at 85-100 ℃ for 30-60 min, cooling to a proper temperature (33-38 ℃ or 50-55 ℃) for producing hydrogen through dark fermentation, and then carrying out anaerobic acclimation and enrichment for 24-36 h (or until the system does not produce hydrogen) under the conditions that the glucose concentration is 0.5-2 g/L, the medium temperature is 33-38 ℃ or the high temperature is 50-55 ℃ to obtain an inoculum for the hydrogen production reaction through dark fermentation;
(3) preparing simulated organic wastewater, and adding hydrogen production inoculum to form a dark fermentation hydrogen production system. The organic wastewater can be prepared by taking glucose, starch, fructose and the like as carbon sources, and the concentration of the organic wastewater is 5-15 g/L. The organic wastewater can be peptone, yeast powder, fish meal and the like as nitrogen sources, and the concentration is 0.05-0.15 g/L. The concentration ratio of the carbon source to the nitrogen source in the added substrate is 30-90: 1;
(4) adding manganese-doped magnetic carbon into the hydrogen produced by dark fermentation. The input amount of the manganese-doped magnetic carbon is 100-1000 mg/L;
(5) and after the steps are completed, performing a dark fermentation hydrogen production experiment, and collecting gas. The reactors used in the dark fermentation experiment are respectively sealed by rubber plugs and connected with a gas collecting device; sealing the reactor and carrying out anaerobic treatment; and the temperature of the water bath temperature control system is adjusted. Fermenting at 33-38 ℃ or 50-55 ℃ for 30-48 h (or until gas production is stopped), and collecting gas by adopting an alkali discharge (8-12% NaOH) method;
the dark fermentation hydrogen production experiment is carried out in a water bath temperature control system; the temperature of the fermentation hydrogen production system is medium temperature (33-38 ℃) or high temperature (50-55 ℃).
Example 1
Manganese-doped magnetic carbon:
a. 1.5g of MnCl2·4H2O and 4.1g FeCl3·6H2Dissolving the O particles in 150ml of deionized water, adding 24g of activated carbon, and stirring for 1.5h to fully and uniformly mix the mixture to obtain the iron-manganese-carbon mixed solution. MnCl2The concentration of the solution is 10 g/L; FeCl3The concentration is 27 g/L; the concentration of the activated carbon is 160 g/L;
b. carrying out oil bath heating reflux reaction on the mixed solution in a reactor, wherein the reactor is connected with a condensation reflux pipe; after the mixed solution is boiled, 50ml of NaOH (50g/L) solution is quickly added into the mixed solution and is stirred and mixed evenly;
c. boiling the mixed solution at 105 ℃, refluxing and reacting for 3 hours, pouring into a beaker after the reaction is completed, and cooling;
d. and drying the mixed solution obtained in the step at the temperature of 85 ℃ for 10 hours to obtain the manganese-doped magnetic carbon.
The prepared material was analyzed and characterized, with the following characterization results (fig. 1-2):
the X-ray diffraction pattern of FIG. 1 shows that characteristic peaks appear at 29.68 °, 34.91 °, 52.71 ° and 56.12 °, together with MnFe2O4Corresponding; at 29.96 °, 32.80 °, 60.895 ° and 67.72 ° with Fe2O3Corresponding; no obvious characteristic peaks appear at 24.27 degrees, 31.38 degrees and 51.68 degrees, which indicates that the material contains trace MnCO3(ii) a In addition, when the 2 theta is 24-28 degrees, weak peaks appear, and the representative material contains activated carbon.
The elemental analysis of manganese-doped magnetic carbon is shown in fig. 2. Elemental analysis showed that the atomic percentages of C, O, Fe and Mn were 79.44%, 18.51%, 1.4% and 0.65%, respectively.
Example 2
Manganese-doped magnetic carbon:
a. 1g of MnCl2·4H2O and 2.6g FeCl3·6H2Dissolving O particles in 150ml of deionized water, adding 12g of activated carbon, stirring for 1h, and ensuring that the activated carbon and the activated carbon are fully and uniformly mixed to obtain the iron-manganese-carbon mixed solution. MnCl2The concentration of the solution is 6.7 g/L; FeCl3The concentration is 14.4 g/L; the concentration of the activated carbon is 80 g/L;
b. the mixed liquid is subjected to oil bath heating reflux reaction in a reactor, and the reactor is connected with a condensation reflux pipe. After the solution is boiled, 50ml of 20g/L NaOH solution is quickly added into the mixed solution and stirred and mixed evenly;
c. boiling the mixed solution at 100 ℃, refluxing and reacting for 2 hours, pouring the mixed solution into a beaker after the reaction is completed, and cooling;
d. and drying the mixed solution obtained in the step for 15h at the temperature of 75 ℃ to obtain the manganese-doped magnetic carbon.
The prepared material is analyzed and characterized, and the XRD pattern has characteristic peaks at 29.68 degrees, 34.91 degrees, 52.71 degrees and 56.12 degrees, and the characteristic peaks and MnFe2O4Corresponding; at 29.96 °, 32.80 °, 60.89 ° and 67.72 ° with Fe2O3Corresponding; weak peaks appeared at 24.27 °, 31.38 ° and 51.68 °, indicating that the material contains trace amount of MnCO3(ii) a In addition, when the 2 theta is 24-28 degrees, a steamed bread peak appears, and the representative material contains activated carbon.
Elemental analysis of manganese-doped magnetic carbon showed that C, O, Fe and Mn were 80%, 19%, 1.8%, and 0.7% in atomic percentage, respectively. .
Example 3
Manganese-doped magnetic carbon:
a. 3g of MnCl2·4H2O and 7.8g FeCl3·6H2Dissolving the O particles in 150ml of deionized water, adding 36.4g of activated carbon, and stirring for 2 hours to fully and uniformly mix the particles to obtain the iron-manganese-carbon mixed solution. MnCl2The concentration of the solution is 20 g/L; FeCl3The concentration is 52 g/L; the concentration of the activated carbon is 242.7 g/L;
b. the mixed liquid is subjected to oil bath heating reflux reaction in a reactor, and the reactor is connected with a condensation reflux pipe. After the mixed solution is boiled, 50ml of 100g/L NaOH solution is quickly added into the boiled mixed solution and is stirred and uniformly mixed;
c. boiling the mixed solution at 120 ℃, refluxing and reacting for 3 hours, pouring the mixed solution into a beaker after the reaction is completed, and cooling;
d. and drying the mixed solution obtained in the step for 20 hours at the temperature of 85 ℃ to obtain the manganese-doped magnetic carbon.
The prepared material is analyzed and characterized, and an XRD (X-ray diffraction) spectrum shows that characteristic peaks appear at 29.68 degrees, 34.91 degrees, 52.71 degrees and 56.12 degrees and correspond to MnFe2O 4; corresponds to Fe2O3 at 29.96 °, 32.80 °, 60.895 °, and 67.72 °; weak peaks appear at 24.27 °, 31.38 ° and 51.68 °, indicating that the material contains trace amounts of MnCO 3; in addition, when the 2 theta is 24-28 degrees, a steamed bread peak appears, and the representative material contains activated carbon.
Elemental analysis of manganese-doped magnetic carbon showed that C, O, Fe and Mn were 79%, 18%, 2%, and 1% in atomic percentage, respectively.
Example 4
Manganese-doped magnetic carbon:
a. 1.7g of MnSO4·H2O and 4g Fe2(SO4)3The particles are dissolved in 150ml of deionized water, 24g of active carbon is added, and the mixture is stirred for 2 hours to be fully and uniformly mixed, so that the iron-manganese-carbon mixed solution is obtained. MnSO4The concentration of the solution is 11.3 g/L; fe2(SO4)3The concentration is 26.7 g/L; the concentration of the activated carbon is 160 g/L;
b. the mixed liquid is subjected to oil bath heating reflux reaction in a reactor, and the reactor is connected with a condensation reflux pipe. After the mixed solution is boiled, 50ml of 100g/L NaOH solution is quickly added into the boiled mixed solution and is stirred and uniformly mixed;
c. boiling the mixed solution at 120 ℃, refluxing and reacting for 3 hours, pouring the mixed solution into a beaker after the reaction is completed, and cooling;
d. and drying the mixed solution obtained in the step for 20 hours at the temperature of 85 ℃ to obtain the manganese-doped magnetic carbon.
Example 5
Manganese-doped magnetic carbon:
a. 2.43g of Mn (NO)3)2·4H2O and 8g Fe (NO)3)3·9H2Dissolving the O particles in 150ml of deionized water, adding 24g of activated carbon, and stirring for 2 hours to fully and uniformly mix the O particles and the activated carbon to obtain the iron-manganese-carbon mixed solution. Mn (NO)3)2The concentration of the solution is 16.2 g/L; fe (NO)3)3The concentration is 53 g/L; the concentration of the activated carbon is 160 g/L;
b. the mixed liquid is subjected to oil bath heating reflux reaction in a reactor, and the reactor is connected with a condensation reflux pipe. After the mixed solution is boiled, 50ml of 100g/L NaOH solution is quickly added into the mixed solution and is stirred and uniformly mixed;
c. boiling the mixed solution at 120 ℃, refluxing and reacting for 3 hours, pouring the mixed solution into a beaker after the reaction is completed, and cooling;
d. and drying the mixed solution obtained in the step for 20 hours at the temperature of 85 ℃ to obtain the manganese-doped magnetic carbon.
Example 6
Middle-temperature glucose hydrogen production fermentation experiment:
A. taking dewatered sludge of an urban sewage treatment plant, and carrying out anaerobic standing for 30d at medium temperature (33-38 ℃) to screen and enrich anaerobic fermentation bacteria;
B. carrying out heat treatment on the enriched sludge at 80 ℃ for 60min, cooling to the appropriate temperature (33-38 ℃) for producing hydrogen through medium-temperature dark fermentation, and then carrying out anaerobic acclimation and enrichment for 24h (or until the system does not produce hydrogen) under the conditions that the glucose concentration is 1g/L and the medium temperature is 33-38 ℃ to obtain an inoculum for producing hydrogen through dark fermentation;
C. respectively pouring five parts of 2.5g of glucose, 0.05g of peptone and 100ml of hydrogen production inoculum into a fermentation reactor, and numbering 1-5;
D. adding 100 mg, 200 mg, 300 mg and 400mg of manganese-doped magnetic carbon into a No. 2-5 reactor in sequence. Diluting all reactors to a constant volume of 500ml by using deionized water, wherein the concentration of glucose in the reactor is 5g/L, the concentration of peptone is 0.1g/L, the proportion of hydrogen production inoculum to the total volume of fermentation is 20%, and the concentration of manganese-doped magnetic carbon is 0-800 mg/L;
E. sealing the reactors with rubber plugs respectively, and connecting the reactors with a gas collecting device; sealing the reactor and carrying out anaerobic treatment; and (3) adjusting the temperature of a water bath temperature control system, wherein the fermentation temperature is 33-38 ℃, the fermentation time is 36 hours (or until gas production is stopped), and collecting the gas by adopting an alkali discharge (8% NaOH) method.
Example 7
Middle-temperature glucose hydrogen production fermentation experiment:
A. taking dewatered sludge of an urban sewage treatment plant, and carrying out anaerobic standing for 15-35 d at medium temperature (33-38 ℃) to screen and enrich anaerobic fermentation bacteria;
B. carrying out heat treatment on the enriched sludge at 90 ℃ for 45min, cooling to the appropriate temperature (33-38 ℃) for producing hydrogen through fermentation, and then carrying out anaerobic acclimation and enrichment for 30h (or until the system does not produce hydrogen) under the conditions that the glucose concentration is 0.5g/L and the medium temperature is 33-38 ℃ to obtain an inoculum for producing hydrogen through dark fermentation;
C. respectively pouring five parts of 5g of glucose, 0.1g of peptone and 150ml of hydrogen-producing inoculum into an anaerobic fermentation reactor, and numbering 1-5;
D. weighing 100 mg, 200 mg, 300 mg and 400mg of manganese-doped magnetic carbon, and sequentially adding the manganese-doped magnetic carbon into a No. 2-5 reactor. Diluting all reactors to a constant volume of 500ml by using deionized water, wherein the concentration of glucose in the reactor is 10g/L, the concentration of peptone is 0.2g/L, the proportion of hydrogen production inoculum to the total volume of fermentation is 30%, and the concentration of manganese-doped magnetic carbon is 0-800 mg/L;
E. sealing the reactors with rubber plugs respectively, and connecting the reactors with a gas collecting device; sealing the reactor and carrying out anaerobic treatment; and (3) adjusting the temperature of a water bath temperature control system, wherein the fermentation temperature is 33-38 ℃, the fermentation time is 30 hours (or until gas production is stopped), and collecting the gas by adopting an alkali discharge (10% NaOH) method.
The hydrogen production effect was analyzed, and the analysis results (fig. 3) were as follows:
during the moderate temperature dark fermentation process of glucose, the hydrogen production is respectively improved by 9.6%, 19.3%, 18.1% and 18.8% when the manganese-doped magnetic carbon is added, wherein the hydrogen production is 193, 211, 208 and 209ml/g glucose when the manganese-doped magnetic carbon is 200, 400, 600 and 800 mg/L. In addition, the highest accumulated hydrogen amount and the highest hydrogen production rate after 9 hours of fermentation are obtained by adding the fermentation system with the concentration of 400mg/L, and the gas amount and the hydrogen production rate are 1055ml and 17.2 ml/(g.h) respectively.
Example 8
High-temperature glucose hydrogen production fermentation experiment:
A. taking dewatered sludge of an urban sewage treatment plant, and carrying out anaerobic standing for 15-35 d at high temperature (50-55 ℃) to screen and enrich anaerobic fermentation bacteria;
B. performing heat treatment on the enriched sludge at 90 ℃ for 45min, cooling to a proper temperature (50-55 ℃) for producing hydrogen through fermentation, and performing anaerobic acclimation and enrichment for 30h (or until a system does not produce hydrogen) under the conditions that the concentration of glucose is 1g/L and the temperature is 50-55 ℃ to obtain an inoculum for producing hydrogen through dark fermentation;
C. respectively pouring five parts of 5g of glucose, 0.1g of peptone and 150ml of hydrogen production inoculum into a fermentation reactor, and numbering 1-5;
D. weighing 100 mg, 200 mg, 300 mg and 400mg of manganese-doped magnetic carbon, and sequentially adding the manganese-doped magnetic carbon into a No. 2-5 reactor. Diluting all reactors to a constant volume of 500ml by using deionized water, wherein the concentration of glucose in the reactor is 10g/L, the concentration of peptone is 0.2g/L, the proportion of hydrogen production inoculum to the total volume of fermentation is 30%, and the concentration of manganese-doped magnetic carbon is 0-800 mg/L;
E. sealing the reactors with rubber plugs respectively, and connecting the reactors with a gas collecting device; sealing the reactor and carrying out anaerobic treatment; and (3) adjusting the temperature of a water bath temperature control system, wherein the fermentation temperature is 50-55 ℃, the fermentation time is 30h (or until gas production is stopped), and collecting the gas by adopting an alkali discharge (10% NaOH) method.
The hydrogen production effect was analyzed, and the analysis results (fig. 4) were as follows:
in the high-temperature fermentation process of glucose, 200-800 mg/L manganese-doped magnetic carbon is added, so that the hydrogen yield in high-temperature fermentation is increased from 123ml/g to 133 ml/g, 148 ml/g and 145ml/g glucose; compared with a control group (without adding manganese-doped magnetic carbon), the 600mg/L manganese-doped magnetic carbon can improve the hydrogen yield by 55.8 percent. When the concentration of the manganese-doped magnetic carbon is 600mg/L, the accumulated hydrogen yield reaches the highest value, namely 740 ml; the maximum hydrogen production rate is 11.7 ml/(g.h) after 9 h; the maximum hydrogen production was 72% higher than the control.
Example 9
High-temperature glucose hydrogen production fermentation experiment:
A. taking dewatered sludge of an urban sewage treatment plant, and carrying out anaerobic standing for 15-35 d at high temperature (50-55 ℃) to screen and enrich anaerobic fermentation bacteria;
B. carrying out heat treatment on the enriched sludge at 100 ℃ for 30min, cooling to a proper temperature (50-55 ℃) for producing hydrogen by dark fermentation, and then carrying out anaerobic acclimation and enrichment for 36h (or until the system does not produce hydrogen) under the conditions that the glucose concentration is 2g/L and the high temperature is 50-55 ℃ to obtain an inoculum for producing hydrogen by dark fermentation;
C. respectively pouring five parts of 7.5g of glucose, 0.15g of peptone and 200ml of hydrogen-producing inoculum into a fermentation reactor, and numbering 1-5;
D. adding 100 mg, 200 mg, 300 mg and 400mg of manganese-doped magnetic carbon into a No. 2-5 reactor in sequence. Diluting all reactors to a constant volume of 500ml by using deionized water, wherein the concentration of glucose in the reactor is 15g/L, the concentration of peptone is 0.3g/L, the proportion of hydrogen production inoculum to the total volume of fermentation is 40%, and the concentration of manganese-doped magnetic carbon is 0-800 mg/L;
E. sealing the reactors with rubber plugs respectively, and connecting the reactors with a gas collecting device; sealing the reactor and carrying out anaerobic treatment; and (3) adjusting the temperature of a water bath temperature control system, wherein the fermentation temperature is 50-55 ℃, the fermentation time is 48 hours (or until gas production is stopped), and collecting the gas by adopting an alkali discharge (12% NaOH) method.
Claims (8)
1. The method for promoting high-temperature dark fermentation hydrogen production by using manganese-doped magnetic carbon is characterized in that the manganese-doped magnetic carbon mainly comprises active carbon and MnFe2O4、Fe2O3And MnCO3Wherein MnFe2O4、Fe2O3And MnCO3The modified activated carbon is uniformly attached to the surface and in the aperture of the activated carbon, and the atomic percentages of C, O, Fe and Mn are respectively 79-80%, 18-19%, 1-2% and 0.5-1%;
the dark fermentation method comprises the following steps:
A. taking dewatered sludge of an urban sewage treatment plant, and carrying out anaerobic standing for 15-35 d under a high-temperature condition to screen and enrich anaerobic fermentation bacteria; the high-temperature condition is 50-55 ℃;
B. carrying out heat treatment on the enriched sludge at 85-100 ℃ for 30-60 min, cooling to the appropriate temperature of 50-55 ℃ for hydrogen production by dark fermentation, and then carrying out anaerobic acclimation and enrichment for 24-36 h under the conditions that the glucose concentration is 0.5-2 g/L and the temperature is 50-55 ℃ to obtain an inoculum for hydrogen production by dark fermentation;
C. respectively pouring five parts of 2.5-7.5 g of glucose, 0.05-0.15 g of peptone and 100-200 ml of hydrogen-producing inoculum into a fermentation reactor, and numbering 1-5;
D. weighing 100 mg, 200 mg, 300 mg and 400mg of manganese-doped magnetic carbon, and sequentially adding the manganese-doped magnetic carbon into a No. 2-5 reactor; diluting all reactors to a constant volume of 500ml with deionized water, wherein the concentration of glucose in the reactor is 5-15 g/L, the concentration of peptone is 0.1-0.3 g/L, the proportion of hydrogen production inoculum to the total volume of fermentation is 20-40%, and the concentration of manganese-doped magnetic carbon is 0-800 mg/L;
E. sealing the fermentation reactors with rubber plugs respectively, and connecting the fermentation reactors with a gas collecting device; sealing the reactor and carrying out anaerobic treatment; and (3) adjusting the temperature of a water bath temperature control system, wherein the fermentation temperature is 50-55 ℃, the fermentation time is 30-48 h, and collecting gas by adopting an alkali discharge method.
2. As claimed inSolving 1 the method for promoting the production of hydrogen by dark fermentation by using the manganese-doped magnetic carbon, which is characterized in that the X-ray diffraction pattern of the manganese-doped magnetic carbon shows that characteristic peaks appear at 29.68 degrees, 34.91 degrees, 52.71 degrees and 56.12 degrees, and the characteristic peaks and MnFe2O4Corresponding; characteristic peaks and Fe appearing at 29.96 °, 32.80 °, 60.895 ° and 67.72 °2O3Corresponding; the characteristic peaks appear at 24.27 degrees, 31.38 degrees and 51.68 degrees, which indicates that the material contains trace MnCO3(ii) a When the 2 theta is 24-28 degrees, a peak appears, and the representative material contains activated carbon.
3. The method for promoting hydrogen production by dark fermentation by using manganese-doped magnetic carbon as claimed in claim 1, wherein the manganese-doped magnetic carbon is obtained by heating a manganese salt and an iron salt in an oil bath under an alkaline condition to perform a condensation reflux reaction, and drying.
4. The method for promoting hydrogen production by dark fermentation by using manganese-doped magnetic carbon as claimed in any one of claims 1 to 3, characterized by preparing the manganese-doped magnetic carbon by adopting the following technical scheme:
manganese ions and iron ions are subjected to oil bath heating in a condensation reflux reactor under the alkaline condition to rapidly react to generate MnFe2O4(ii) a The residual iron ions in the solution react with hydroxide ions to generate ferric hydroxide, and the ferric hydroxide dehydrates under the heating condition to form Fe2O3(ii) a The residual manganese ions in the solution react with CO in the air under the alkaline condition2Reacting to generate trace MnCO3Continuously heating until the reaction is completed, and then MnFe2O4、Fe2O3And trace MnCO3Uniformly attaching the manganese-doped magnetic carbon on the surface and in the pore diameter of the active carbon, and drying to obtain the manganese-doped magnetic carbon; heating in the oil bath, wherein the reaction temperature is 100-130 ℃, and the reaction time is 2-4 h; the drying is carried out at the drying temperature of 60-85 ℃ for 10-20 h.
5. The method for promoting dark fermentation to produce hydrogen by using manganese-doped magnetic carbon as claimed in claim 4, wherein manganese salt and iron salt are used as raw materials, and the manganese salt is one or more of manganese chloride, manganese sulfate, manganese nitrate or manganese phosphate; the ferric salt is one or more of ferric chloride, ferric sulfate, ferric nitrate or ferric acetate;
the alkaline condition is obtained by adjusting the pH value of the NaOH solution to 10-12.
6. The method for promoting hydrogen production by dark fermentation by using manganese-doped magnetic carbon as claimed in claim 5, wherein the molar ratio of manganese to iron to carbon is 1:2: 50-150, and the concentration of manganese salt is 3.75-37.5 g/L; the concentration of the ferric salt is 10.5-102 g/L; the concentration of the activated carbon is 45-450 g/L; the concentration of the NaOH solution is 20-129 g/L.
7. The method for promoting hydrogen production by dark fermentation by using manganese-doped magnetic carbon as claimed in any one of claims 4 to 6, wherein the preparation method of the manganese-doped magnetic carbon comprises the following specific steps:
(1) manganese chloride, ferric chloride and active carbon are used as raw materials to prepare a ferro-manganese-carbon mixed solution;
(2) heating the mixed solution obtained in the step (1) in an oil bath until the mixed solution is boiled, quickly adding a NaOH solution, and stirring and uniformly mixing;
(3) keeping boiling reaction at a certain temperature, pouring the reaction product into a beaker for cooling after the reaction is completed;
(4) and drying the mixed solution obtained in the step at a certain temperature to obtain the manganese-doped magnetic carbon.
8. The method for promoting hydrogen production by dark fermentation by using manganese-doped magnetic carbon as claimed in claim 7, wherein the preparation steps of the iron-manganese-carbon mixed solution in the step (1) are as follows:
1-3 g of MnCl2·4H2O and 2.6-7.8 g FeCl3·6H2Dissolving O particles in 100-200 ml of deionized water, adding 12-36.4 g of activated carbon, and stirring for 1-2 hours to fully mix the O particles uniformly to obtain a ferro-manganese-carbon mixed solution; at this time, MnCl2The concentration of the solution is 5-30 g/L, FeCl3The concentration is 13-78 g/L, and the concentration of the active carbon is 60-364 g/L;
the oil bath method in step (2) is as follows:
the mixed solution is carried out in a reactor, and the reactor is connected with a condensation reflux pipe; quickly adding NaOH solution after the solution is boiled, and uniformly stirring;
the preparation method of the NaOH solution in the step (2) is as follows:
dissolving 1.3-6.45 g of NaOH particles in 50ml of deionized water to obtain an alkali liquor with the pH value of 10-12, wherein the concentration of NaOH is 34.4-129 g/L;
keeping the boiling reaction time of the step (3) to be 1-2 h;
the drying temperature in the step (4) is 60-85 ℃, and the drying time is 10-20 h.
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