CN109621703B - For enhanced biological removal of H2S iron oxide-biochar composite material and preparation method thereof - Google Patents

For enhanced biological removal of H2S iron oxide-biochar composite material and preparation method thereof Download PDF

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CN109621703B
CN109621703B CN201910026851.6A CN201910026851A CN109621703B CN 109621703 B CN109621703 B CN 109621703B CN 201910026851 A CN201910026851 A CN 201910026851A CN 109621703 B CN109621703 B CN 109621703B
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iron oxide
composite material
biochar composite
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biological removal
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CN109621703A (en
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江霞
靳紫恒
蒋文举
汪华林
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Sichuan University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/84—Biological processes
    • B01D53/85—Biological processes with gas-solid contact
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/52—Hydrogen sulfide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

The invention belongs to the field of environmental protection, and relates to a method for strengthening biological removal of H2Iron oxide-organisms of SA carbon composite material and a preparation method thereof. The method adopts waste biomass, iron-containing substances, a binder and distilled water as raw materials, and prepares the iron oxide-biochar composite material after uniformly mixing, molding, carbonizing and activating the raw materials. The iron oxide-biochar composite material obtained by the invention is used as the filler of a biological desulfurization system, has the advantages of low raw material cost, good adsorption performance, easy film formation, rich active point positions, long service life and the like, and can simultaneously realize the effect of biochar on H2Adsorption/desorption of S, iron oxide on H2Solid/liquid phase catalytic oxidation of S, regeneration of iron element and microbial pair of H2The degradation and biological regeneration of S realize the self-circulation of the system, improve the stability of the system, ensure that the system has short starting time and can bear the H with high load2S, can be quickly recovered after a long-term hunger period, and strengthens the microbial pair H2And (4) removing effect of S.

Description

For enhanced biological removal of H2S iron oxide-biochar composite material and preparation method thereof
Technical Field
The invention belongs to the field of environmental protection, and particularly relates to a method for strengthening biological removal of H2S iron oxide-biochar composite material and a preparation method thereof.
Background
Energy gases such as methane, natural gas and the like are used as important clean energy, are important components and key links for energy conservation and emission reduction, and play a great role in coping with climate change, developing low-carbon economy and promoting new rural construction. However, during the production of biogas and the exploitation of natural gas, H is often accompanied2And (4) generation of S gas. H2S is a harmful highly toxic gas, and the concentration in the air is over 28mg/m3When the work is finished, people can not work normally; over 1000mg/m3In time, acute poisoning may occur, causing death of the person. Furthermore, H2S has strong corrosion effect on pipelines, burners, instruments and meters and the like, and H is generated after combustion2SO formed by S2Can cause environmental pollution and serious acidRain, haze and other pollution problems. Usually, H in biogas2The concentration of S is 100-15000 mg/m3H in natural gas of China2S content over 10000mg/m3The natural gas accounts for 25 percent of the total reserve and is far higher than the regulation of the national environmental protection standard by 20mg/m3. The research and development of the desulfurization technology are particularly urgent for realizing the environmental protection, high-value and high-efficiency utilization of energy gas and building an environmental-friendly sewage treatment plant.
The conventional desulfurizing agent mainly comprises activated carbon and iron oxide. The active carbon can achieve the aim of desulfurization through a developed pore structure and the physical/chemical adsorption effect of surface active groups, has good mechanical property, and can be desulfurized at normal temperature. However, when the adsorption of the activated carbon desulfurization agent reaches a certain level, the desulfurization efficiency is lowered, and replacement or regeneration is necessary. Iron oxide desulfurization is still widely applied to desulfurization processes of coal gas, natural gas, synthetic feed gas and methane gas to date due to the advantages of simple process, high reaction rate, low price and outstanding purification degree. However, the iron oxide desulfurization has the problems of short service life, high cost and the like, and the deactivated desulfurizer needs to be replaced periodically or Fe is regenerated by adopting a regeneration method such as an electrochemical method or an oxidant2+Is oxidized into Fe3+. In the investigation of 265 family rural biogas digesters of 8 provinces such as Sichuan, the desulfurizing agent is not replaced by most biogas users due to the complicated regeneration or replacement operation of the desulfurizing agent, which seriously affects the desulfurizing effect and the service life of equipment.
In addition to the above two commonly used desulfurizers, the liquid phase catalytic method (also called alkali liquor absorption method) which is most widely used in China at present can avoid the defect of difficult chemical absorption and regeneration, but has the disadvantages that the consumption of chemicals is increased by-products, the treatment of harmful waste liquid is difficult, and finally discharged gas is easy to carry sulfur-containing alkali-containing liquid drops, and the discharge of tail gas with the liquid drops can become PM2.5The hidden trouble of formation aggravates haze weather pollution.
Biological desulfurization is a clean desulfurization technology which is developed rapidly in recent years. The metabolism of microorganism can be used for realizing H2S gas is converted into elemental sulfur or sulfate, and finally H is removed2Purpose of S, having removalHigh efficiency, low energy consumption, environmental protection, cleanness and the like. In recent years, biological desulfurization process has been successfully used in energy gas and better desulfurization effect, H2The removal rate of S can reach more than 95 percent, such as oxidizing H by using thiobacillus alcanidum2The energy released during S can be used by the cell to immobilize CO2Growing while removing CO from the source gas2The calorific value is improved. However, it was found that when H2When the S concentration load fluctuates, the biological desulfurization performance is seriously deteriorated. Instability in operation is the biggest defect of biological desulfurization, so that proper fillers are selected to support and buffer microorganisms.
Common biological fillers mainly include both types of organic fillers and inorganic fillers. The organic filler mainly comprises high molecular polymers such as polyvinyl chloride, polystyrene, polyamide and the like, and the high molecular polymer filler does not have the adsorption capacity on pollutants, so that the removal performance on the pollutants is low. The inorganic filler mainly comprises granular activated carbon, molecular sieve, furnace slag and the like, has better film-forming performance, has a certain adsorption effect on pollutants, can strengthen the degradation capability of microorganisms, and particularly has the advantages of short retention time, small reactor, high efficiency, impact load resistance, easy film formation and the like when the activated carbon is used as the filler, but the inorganic filler has the characteristics of easy adsorption saturation and timely regeneration.
CN107021561A discloses a biological deodorization filler with physical, chemical and biological synergistic effects, which adopts volcanic rock and pyrite as upper-layer filler and shells as lower-layer filler. Although the microorganisms loaded on the pyrite can promote the circulation of iron ions, the pyrite has poor self-supporting strength and can cause higher bed pressure drop, and the mixed filler is distributed in a layered mode to cause the problem of uneven distribution of biological membranes.
Disclosure of Invention
For existing removal of H2S, the invention provides a method for strengthening biological removal of H2S iron oxide-biochar composite material and a preparation method thereof. The iron oxide-biochar composite material can be used for biological removalH2The filler of S is used, and has good effect.
The first technical problem to be solved by the invention is to provide a method for enhancing biological removal of H2A preparation method of the S iron oxide-biochar composite material. The preparation method comprises the following steps:
a. according to the weight ratio, 5-10 parts of biomass raw material, 0.1-2 parts of iron-containing substance, binder and water are fully mixed, the mixture is molded to obtain a finished body, and the finished body is dried;
b. heating the dried adult to 400-600 ℃ in an inert atmosphere, and preserving the temperature to obtain a carbonized material;
c. and (3) physically activating the carbonized material to obtain the iron oxide-biochar composite material.
Preferably, the above-mentioned method is used for enhanced biological removal of H2In the step a of the preparation method of the iron oxide-biochar composite material, 2-5 parts of the binder are used.
Preferably, the above-mentioned method is used for enhanced biological removal of H2In the step a of the preparation method of the iron oxide-biochar composite material, 0.5-1 part of water is used.
Wherein the above is used for enhanced biological removal of H2In the step a of the preparation method of the iron oxide-biochar composite material, the iron-containing substance is at least one of limonite, hematite, magnetite, goethite, pyrolusite, ferric oxide or ferroferric oxide.
Further, the above method for enhanced biological removal of H2In step a of the preparation method of the iron oxide-biochar composite material of S, the main component of the limonite, hematite, magnetite, goethite or pyrolusite is metallic iron oxide, such as Fe2O3、Fe3O4Or FeOOH, Fe content greater than 30%3+The content accounts for more than 50% of the total iron content.
Wherein the above is used for enhanced biological removal of H2In the step a of the preparation method of the iron oxide-biochar composite material, the biomass raw material is at least one of wood chips, coconut shells, fruit shells, bamboo powder, straws, sludge or vinasse.
Wherein the above is used for enhanced biological removal of H2In the step a of the preparation method of the iron oxide-biochar composite material, the biomass raw material is waste biomass.
Further, the above method for enhanced biological removal of H2In the step a of the preparation method of the iron oxide-biochar composite material, the biomass raw material is undersize materials which are sieved by a 100-200-mesh sieve.
Further, the above method for enhanced biological removal of H2In the step a of the preparation method of the iron oxide-biochar composite material, the iron-containing substances are undersize materials which are sieved by a sieve with 100-200 meshes.
Wherein the above is used for enhanced biological removal of H2In the step a of the preparation method of the iron oxide-biochar composite material, the binder is at least one of coal tar, humic acid, PVB or polyvinyl alcohol.
Wherein the above is used for enhanced biological removal of H2In the step a of the preparation method of the iron oxide-biochar composite material, the shape of the mold used for molding is a cylinder.
Further, the above method for enhanced biological removal of H2In the step a of the preparation method of the iron oxide-biochar composite material, the diameter of the cylinder is 2-8 mm, and the length of the cylinder is 5-20 mm.
Wherein the above is used for enhanced biological removal of H2In step a of the preparation method of the iron oxide-biochar composite material, drying is carried out until the water content is below 2%.
Further, the above method for enhanced biological removal of H2In the step a of the preparation method of the S iron oxide-biochar composite material, the drying is carried out for more than 24 hours at the temperature of 80-105 ℃.
Wherein the above is used for enhanced biological removal of H2In the step b of the preparation method of the iron oxide-biochar composite material, the inert atmosphere is nitrogen or helium.
Wherein the above is used for enhanced biological removal of H2In the step b of the preparation method of the S iron oxide-biochar composite material, the temperature is increased to 400-600 DEG CThe speed is 5-10 ℃/min.
Wherein the above is used for enhanced biological removal of H2In the step b of the preparation method of the iron oxide-biochar composite material, the heat is preserved for 1-4 hours.
In particular, the above-mentioned method for enhanced biological removal of H2In the step c of the preparation method of the S iron oxide-biochar composite material, the activating agent adopted by physical activation is water vapor, air or CO2At least one of them.
Wherein the above is used for enhanced biological removal of H2In the step c of the preparation method of the iron oxide-biochar composite material, the activation temperature is 600-950 ℃.
Further, the above method for enhanced biological removal of H2In the step c of the preparation method of the iron oxide-biochar composite material, the temperature is increased to 600-950 ℃ at a rate of 5-10 ℃/min.
Wherein the above is used for enhanced biological removal of H2In the step c of the preparation method of the iron oxide-biochar composite material, the activation time is 1-4 h.
The second technical problem to be solved by the present invention is to provide the above-mentioned method for enhanced biological removal of H2Preparation method of S iron oxide-biochar composite material for enhanced biological removal of H2The iron oxide-biochar composite of S.
The third technical problem to be solved by the invention is to provide the above-mentioned method for enhanced biological removal of H2Biological removal of H from S iron oxide-biochar composite2Use as a microbial filler/carrier in S systems.
The invention has the beneficial effects that:
1) the iron oxide-biochar composite material obtained by the invention is used as a filler for a biological desulfurization system, and can be desulfurized from the following four aspects: (1) biomass charcoal pair H2S is adsorbed; the developed pore structure of the biomass charcoal can adsorb H2S, simultaneously providing a good growth place for the microorganisms; (2) iron oxide pair H2S is adsorbed and oxidized; iron oxide as microbial filler/carrierCan obtain higher H than that of molecular sieve and granular porous carbon as biomembrane carrier2S removing effect; (3) microbial (e.g. sulfur oxidizing bacteria SOB) on H2Oxidative degradation of S; degradable and absorbable H of microbial biofilm attached to biochar2S, thereby regenerating the biochar; (4) fe in liquid phase3+To H2Chemical oxidation of S; fe3+Has quite high oxidation-reduction potential and can rapidly convert H2S is oxidized into elemental sulfur, and sulfur resource recovery is realized. As shown in fig. 1. Therefore, the iron oxide-biochar composite material obtained by the invention has the advantages of low raw material cost, good adsorption performance, easy film formation, rich active point positions, long service life and the like when being used as the filler of a biological desulfurization system, and the filler can simultaneously realize the effect of biochar on H2Adsorption/desorption of S, iron oxide on H2Solid/liquid phase catalytic oxidation of S, regeneration of iron element and microbial pair of H2The degradation and biological regeneration of S realize the self-circulation of the system, improve the stability of the system, ensure that the system has short starting time and can bear the H with high load2S, can be quickly recovered after a long-term hunger period, and strengthens the microbial pair H2And (4) removing effect of S. The iron oxide-biochar composite material is used for biological H removal2The microbial carrier/filler of the S system can stably run for more than 120 days at the removal rate of more than 85 percent, thereby greatly improving the biological H removal2Stability of the S system.
2) H removal of the iron oxide-biochar composite material obtained by the invention2At the same time as S, the microorganism can also convert Fe2+Reoxidation to Fe3+The recycling of the elemental sulfur of the desulfurization product is completed, and the iron source is regenerated and recycled. As shown in fig. 2.
3) The iron oxide-biochar composite material has good pore structure, larger specific surface area, stronger adsorption capacity and high H load2When S is present, H can be adsorbed2S, the processing efficiency of the system is greatly improved; and at low load, the adsorbed pollutants can be desorbed for microbial degradation, and self-circulation is realized. Thus, biological dehydrogenation2The stability of the S system is greatly improved.
4) The iron oxide-biochar composite material has a large specific surface area, can provide a good growth place for microorganisms, increases biomass, and can greatly improve the treatment efficiency of the microorganisms.
5) The invention combines natural iron ore rich in iron with biochar to prepare the iron oxide-biochar composite material, can provide rich active sites of iron oxide, and can catalyze H by solid phase/liquid phase2S is oxidized into elemental sulfur to be recycled, and the reaction rate is improved.
6) The iron oxide-biochar composite material provided by the invention has the advantages that waste biomass can be adopted as a raw material, the solid waste of the biomass is recycled, and the cost of the biological filler is greatly reduced.
Drawings
FIG. 1 shows the enhanced biological removal of H from an iron oxide-biochar composite2The S mechanism;
FIG. 2 is a mechanism of the regeneration cycle of the iron catalyst in the microorganism and packing;
FIG. 3 is an XRD pattern of an iron oxide-biochar composite;
FIG. 4 shows the start-up period H of the biological system of activated carbon and iron oxide-biochar composite2S, outlet concentration change;
FIG. 5 shows the starvation period H of the activated carbon and iron oxide-biochar composite biological system2S, outlet concentration change;
FIG. 6 shows the stabilization phase H of the biological system of activated carbon and iron oxide-biochar composite2S, outlet concentration change;
FIG. 7 is a graph of the change in ferrous ion concentration in activated carbon and iron oxide-biochar composite biological systems;
figure 8 is a graph of pH change in activated carbon and iron oxide-biochar composite biological systems;
FIG. 9 shows SO in a biological system of activated carbon and iron oxide-biochar composite4 2-The concentration changes.
Detailed Description
The invention is used for strengthening biological removal of H2The preparation method of the S iron oxide-biochar composite material comprises the following steps:
a. according to the weight ratio, 5-10 parts of biomass raw material, 0.1-2 parts of iron-containing substance, binder and water are fully mixed, the mixture is poured into a mold to be molded to obtain a finished body, and the finished body is dried;
b. putting the dried adult into a tubular furnace, heating to 400-600 ℃ in an inert atmosphere, and preserving heat to obtain a carbonized material;
c. and c, physically activating the carbonized material obtained in the step b to obtain the iron oxide-biochar composite material.
In the step a of the method, in order to ensure the strength of the obtained iron oxide-biochar composite material, the proportion relationship between the biomass raw material and the iron-containing substance is preferably controlled to be 5-10 parts by weight of the biomass raw material and 0.1-2 parts by weight of the iron-containing substance.
In the step a of the method, in order to facilitate more uniform subsequent mixing and forming, the biomass raw material is undersize materials which are sieved by a 100-200-mesh sieve, and the iron-containing materials are undersize materials which are sieved by a 100-200-mesh sieve.
In step a of the method of the present invention, the iron-containing material is at least one of limonite, hematite, magnetite, goethite or pyrolusite, and the main component thereof is metallic iron oxide such as Fe2O3、Fe3O4Or FeOOH, etc., with an iron content of more than 30 wt.%, Fe3+The content is more than 50 wt% of the total iron content. The iron-containing substance may be ferric oxide or ferroferric oxide.
In the step a of the method, the biomass raw material is at least one of sawdust, coconut shells, fruit shells, bamboo powder, straws, sludge or vinasse. In order to impart higher value to the waste material, the biomass feedstock may be selected from waste biomass.
In step a of the method, the binder is at least one of coal tar, humic acid, PVB or polyvinyl alcohol. The purpose of adding the binder is to well bond the biomass raw material and the iron-containing substance, the addition amount of the binder has no special requirement, but in order to ensure sufficient bonding without wasting raw materials and saving the cost of subsequent processes, 2-5 parts by weight of the binder is preferably selected. Similarly, the purpose of adding water is to fully mix the biomass raw material and the iron-containing substance, the addition amount of water has no special requirement, but in order to ensure full mixing, avoid waste of the raw material and save the cost of subsequent processes, 0.5-1 part by weight of water is preferred.
In the step a of the method, the shape, the size and the dimension of the mold adopted by molding have no special requirements, and the mold can be selected arbitrarily according to the requirements. Further, the mold is cylindrical in shape. Furthermore, the diameter of the cylinder is 2-8 mm, and the length of the cylinder is 5-20 mm.
In step a of the method of the invention, the drying is carried out until the water content is below 2 wt%. Further, the drying is carried out for more than 24 hours at the temperature of 80-105 ℃.
In step b of the method of the present invention, during the temperature rise in the absence of oxygen (i.e., in an inert atmosphere such as nitrogen or helium), organic matters such as cellulose and hemicellulose are slowly decomposed to produce biochar. If the temperature rise rate is too fast, the high-temperature fast pyrolysis is carried out, and the main products are by-products such as synthesis gas, liquid tar and the like. Therefore, the heating rate is preferably controlled to be 5-10 ℃/min. In order to ensure complete carbonization, the carbonization temperature needs to be controlled to be 400-600 ℃. The heat preservation time is 1-4 h.
In step c of the method, the purpose of activation is to form pores and then add active functional groups to the carbon surface. The activation may be carried out by any activation means conventional in the art, such as physical activation. Further, the activating agent used for physical activation is water vapor, air or CO2Any one of them.
In the step C of the method, the physical activator is adopted to mainly react as gas to enlarge micropores of the carbon at high temperature, and the water vapor can also react with the element C to generate carbon monoxide and hydrogen so as to further form the micropores. The reaction principle of each activator is not the same, but the main purpose is to endow more oxygen-containing functional groups and pore structures on the surface of the biochar, so that the biochar has more active chemical properties and stronger adsorption capacity.
Example 1
According to the weight parts, hematite and wood dust are respectively crushed, ground and sieved by a 200-mesh sieve; 10 parts of wood dust, 2 parts of hematite, 5 parts of humic acid and distilled water1 part of the mixture is fully mixed, the mixture is poured into a grinding tool to be formed into a formed body, and the formed body is dried for more than 24 hours at 105 ℃; placing the dried adult in a tubular furnace, heating to 600 ℃ at the speed of 5 ℃/min under an inert atmosphere, and keeping the temperature for 2.0 hours to obtain a carbonized material; continuously heating the tube furnace to 950 ℃ at the speed of 5 ℃/min, and introducing CO2Activation for 1.0h, followed by cooling to room temperature under an inert atmosphere, yielded iron oxide-biochar composite (LAC). As shown in fig. 3, the iron oxide-biochar composite LAC has a characteristic peak of ferroferric oxide in an XRD spectrogram.
The LAC prepared by the method is used as a filler and filled in a column type bio-trickling filter, the inner diameter of the reactor is 40mm, and the height of the filler layer is 200 mm. Selecting common equal-volume commercial polypropylene foam filler (PP) and Activated Carbon (AC) as controls, and comparing the three fillers with H in the bio-trickling filter2S processing power.
Domesticated aerobic desulfurization mixed bacteria (SOB) (the strain comes from return sludge of a secondary sedimentation tank of a sewage treatment plant, is a common bacterium in the field, and then Na is adopted2S、Na2S2O3Acclimated to aerobic desulfurization bacteria) was used (component: na (Na)2HPO41.2g/L、 KH2PO41.8g/L、MgSO4·7H2O0.1g/L、NH4Cl0.1g/L、CaCl20.03g/L) were washed several times and then poured into a biotrickling filter filled with LAC packing, and the mixed bacteria were trapped in the bed. The bottom of the trickling filtration tower is provided with a glass circulation tank, and 1.2L of microorganism culture medium (the culture solution) is filled in the circulation tank to be used as the circulation solution of the reactor. The circulating liquid is prepared with the culture medium. The liquid in the circulation tank is conveyed to the top of the column reactor at a flow rate of 5mL/min by a continuously working peristaltic pump, and then the liquid uniformly falls from the top under the action of gravity, passes through the packing bed layer and flows into the circulation tank. Air is blown into the circulating tank by an air pump to realize indirect oxygen supply to the microorganisms. After the reaction had begun, 1000ppmv of H was fed to the top of the reactor2S, the empty bed retention time is 2min, and the outlet H is measured periodically2The concentration of S.
As shown in FIG. 4, NaHCO was used3As a carbon source, when the retention time is 2min, the desulfurization efficiency of each reactor is basically maintained at about 100%, but in the reaction start-up period, PP fluctuates greatly, AC fluctuates slightly, and LAC does not fluctuate obviously. The results show that the reactor loaded with LAC starts up significantly faster within the first 10 days of reactor operation.
Example 2
According to the weight parts, hematite and wood dust are respectively crushed, ground and sieved by a 200-mesh sieve; fully mixing 10 parts of wood chips, 2 parts of hematite, 5 parts of humic acid and 1 part of distilled water; pouring the mixture into a grinding tool to form a finished product; drying the obtained product at 105 deg.C for more than 24 hr; placing the dried adult in a tubular furnace, heating to 600 ℃ at a speed of 10 ℃/min under an inert atmosphere, and keeping the temperature for 1.0 hour to obtain a carbonized material; heating the tube furnace to 900 ℃ at the speed of 10 ℃/min, and introducing CO2Activation for 2.0h, followed by cooling to room temperature under an inert atmosphere, yielded iron oxide-biochar composite (LAC).
Equal volumes of LAC and AC were loaded separately in a bio-trickling filter for comparison of pair H2And (5) processing effect of S. As shown in FIG. 5, when the reaction proceeded for 40 days, the residence time of the original empty bed was shortened to 2min to 1min, and the carbon source was changed to CO2，H2The concentration of S outlet gas was increased but the outlet H of the LAC reactor was loaded2The concentration of S is still lower than that of AC, so that the desulfurization efficiency of the iron oxide-biochar composite material is obviously improved. Even when the introduction of H is stopped2The S gas is aerated again after a period of time, and the outlet H of the LAC reactor is loaded2The reactor, in which the S concentration is still less than that of AC, demonstrates the higher buffering capacity of the LAC packing.
Example 3
According to the weight parts, hematite and wood dust are respectively crushed, ground and sieved by a 200-mesh sieve; fully mixing 10 parts of wood chips, 2 parts of hematite, 5 parts of humic acid and 1 part of distilled water; pouring the mixture into a grinding tool to form a finished product; drying the obtained product at 105 deg.C for more than 24 hr; placing the dried adult in a tubular furnace, heating to 600 ℃ at a speed of 10 ℃/min under an inert atmosphere, and keeping the temperature for 1.0 hour to obtain a carbonized material; heating the tube furnace to 800 ℃ at a speed of 10 ℃/minIntroduction of CO2Activating for 2.0h, and then cooling to room temperature under an inert atmosphere to obtain the iron oxide-biochar composite LAC.
Equal volumes of LAC and AC were loaded separately in a bio-trickling filter for comparison of pair H2And (5) processing effect of S. As shown in FIG. 6, after the reaction was carried out for 95 days, O was added2The oxygen-sulfur ratio was 14.0 by a lift. During the oxygen feed, both reactors had fluctuated, but in the course of the long run the LAC outlet H2The S concentration is still much lower than that of AC, and it is presumed that the Fe content in LAC after oxygen supply is increased2+Can be oxidized into Fe more quickly3+Thereby maintaining a high desulfurization rate. In conclusion, the LAC-loaded reactor has better desulfurization performance and stability under long-term operation.
Example 4
Respectively crushing limonite and coconut shells in parts by weight, grinding and sieving with a 200-mesh sieve; fully mixing 5 parts of coconut shell, 1 part of limonite, 5 parts of polyvinyl alcohol and 1 part of distilled water; pouring the mixture into a grinding tool to form a finished product; drying the obtained product at 105 deg.C for more than 24 hr; placing the dried adult in a tubular furnace, heating to 400 ℃ at a speed of 10 ℃/min under an inert atmosphere, and keeping the temperature for 2.0 hours to obtain a carbonized material; heating the tube furnace to 950 ℃ at the speed of 10 ℃/min, introducing water vapor for activation for 2.0h, and then cooling to room temperature in an inert atmosphere to obtain the iron oxide-biochar composite LAC.
Equal volumes of LAC and AC were loaded separately in a bio-trickling filter for comparison of pair H2S treatment effect, monitoring Fe in reactor2+Concentration, pH, SO4 2-The change in concentration.
As shown in FIG. 7, the ferrous ion concentration in the LAC reactor was higher than that in the AC reactor, indicating that LAC can release Fe in the culture broth2+To participate in the desulfurization reaction and be oxidized into Fe by SOB3+. During reactor starvation (without any media addition), autotrophic bacteria will utilize the quilt H in LAC2Fe produced by reduction of S2+As an electron donor for metabolic activities, and thus Fe2+The concentration immediately dropped. Iron ions can be in the filler through the activity of autotrophic bacteriaRealizing self-circulation, and carrying out autotrophic bacteria to transform Fe2+Oxidation to Fe3 +。
The oxygen introduction is enhanced in the later stage of the operation of the reactor, and the oxygen introduction can promote Fe2+But also easily lead to SO4 2-Accumulation of (2). SO (SO)4 2-Can lead to secondary pollution, and SO4 2-Is a strong acid and weak base salt, SO that SO is directly detected4 2-And indirect detection of pH can both feed back the reactor status. After 70 days of reactor operation, as shown in FIG. 8, it is evident that the pH in the LAC reactor is higher than that of the AC, and from FIG. 9, the SO content is shown4 2-The concentration was always lower than in the AC reactor, demonstrating that H can be more easily controlled when iron oxide is present2Conversion of S to elemental S, while AC reactors more heavily convert H2S is oxidized into SO4 2-。
Example 5
Respectively crushing limonite and coconut shells in parts by weight, grinding and sieving with a 200-mesh sieve; fully mixing 5 parts of coconut shell, 1 part of limonite, 5 parts of coal tar and 1 part of distilled water; pouring the mixture into a grinding tool to form a finished product; drying the obtained product at 105 deg.C for more than 24 hr; placing the dried adult in a tubular furnace, heating to 500 ℃ at a speed of 10 ℃/min under an inert atmosphere, and keeping the temperature for 2.0 hours to obtain a carbonized material; heating the tube furnace to 900 ℃ at the speed of 10 ℃/min, introducing steam for activation for 2.0h, and then cooling to room temperature in an inert atmosphere to obtain the iron oxide/biochar composite LAC.
The prepared LAC was applied to a bio-trickling filter, and the elemental composition of the filler after desulfurization was analyzed in comparison with AC. As shown in Table 1, the S content of LAC was 35.9% and the AC content was 33.1% after 120 days of desulfurization, indicating that the iron oxide-biochar composite was responsible for H2S adsorption and promotion of sulfur recovery.
TABLE 1 elemental analysis of activated carbon and limonite/biochar composites after biological desulfurization
Sample name N C H S C/N C/H
AC 0.54 3.68 4.137 33.087 6.8222 0.8896
LAC 0.78 9.85 2.799 35.909 12.5658 3.5175

Claims (15)

1. For enhanced biological removal of H2The preparation method of the S iron oxide-biochar composite material is characterized by comprising the following steps of: the method comprises the following steps:
a. according to the weight ratio, 5-10 parts of biomass raw material, 0.1-2 parts of iron-containing substance, binder and water are fully mixed, the mixture is molded to obtain a finished body, and the finished body is dried; the iron-containing substance is at least one of limonite, hematite, magnetite, goethite, pyrolusite, ferric oxide or ferroferric oxide;
b. heating the dried adult to 400-600 ℃ in nitrogen or inert atmosphere, and preserving heat to obtain a carbonized material;
c. and (3) physically activating the carbonized material to obtain the iron oxide-biochar composite material.
2. The process of claim 1 for enhanced biological removal of H2The preparation method of the S iron oxide-biochar composite material is characterized by comprising the following steps of: in the step a, 2-5 parts of binder is used; and 0.5-1 part of water.
3. The method according to claim 1 or 2 for enhanced biological removal of H2The preparation method of the S iron oxide-biochar composite material is characterized by comprising the following steps of: in the step a, the biomass raw material is at least one of wood chips, coconut shells, fruit shells, bamboo powder, straws, sludge or vinasse.
4. The method according to claim 1 or 2 for enhanced biological removal of H2The preparation method of the S iron oxide-biochar composite material is characterized by comprising the following steps of: in the step a, the biomass raw material is waste biomass.
5. The method according to claim 1 or 2 for enhanced biological removal of H2The preparation method of the S iron oxide-biochar composite material is characterized by comprising the following steps of: in the step a, the biomass raw material is undersize materials which are sieved by a 100-200-mesh sieve.
6. The method according to claim 1 or 2 for enhanced biological removal of H2The preparation method of the S iron oxide-biochar composite material is characterized by comprising the following steps of: in step a, the limonite, hematite and magnetThe main components of the ore, goethite or pyrolusite are metallic iron oxide, the content of iron is more than 30 percent, and Fe3+The content accounts for more than 50% of the total iron content.
7. The method according to claim 1 or 2 for enhanced biological removal of H2The preparation method of the S iron oxide-biochar composite material is characterized by comprising the following steps of: in the step a, the iron-containing substance is undersize materials which are sieved by a 100-200-mesh sieve.
8. The method according to claim 1 or 2 for enhanced biological removal of H2The preparation method of the S iron oxide-biochar composite material is characterized by comprising the following steps of: in the step a, the binder is at least one of coal tar, humic acid, PVB or polyvinyl alcohol.
9. The process of claim 1 for enhanced biological removal of H2The preparation method of the S iron oxide-biochar composite material is characterized by comprising the following steps of: in the step a, the shape of the mould adopted by the molding is a cylinder.
10. The process of claim 9 for enhanced biological removal of H2The preparation method of the S iron oxide-biochar composite material is characterized by comprising the following steps of: in the step a, the diameter of the cylinder is 2-8 mm, and the length of the cylinder is 5-20 mm.
11. The method according to claim 1 or 2 for enhanced biological removal of H2The preparation method of the S iron oxide-biochar composite material is characterized by comprising the following steps of: in the step (b), the step (c),
the inert atmosphere is helium;
the heating rate is 5-10 ℃/min;
and preserving the heat for 1-4 h.
12. The method according to claim 1 or 2 for enhanced biological removal of H2The preparation method of the S iron oxide-biochar composite material is characterized by comprising the following steps of: in the step c, the step (c),
the activating agent adopted by the physical activation is water vapor, air or CO2At least one of (1);
the activation temperature is 600-950 ℃;
the activation time is 1-4 h.
13. The process of claim 12 for enhanced biological removal of H2The preparation method of the S iron oxide-biochar composite material is characterized by comprising the following steps of: in the step c, the temperature is raised to 600-950 ℃ at a rate of 5-10 ℃/min.
14. Use of any of claims 1 to 13 for enhanced biological removal of H2Preparation method of S iron oxide-biochar composite material for enhanced biological removal of H2The iron oxide-biochar composite of S.
15. The process of claim 14 for enhanced biological removal of H2Biological removal of H from S iron oxide-biochar composite2Use as a microbial filler/carrier in S systems.
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