CN114620832A - Sulfur-based autotrophic microbial denitrification material and preparation and application methods thereof - Google Patents
Sulfur-based autotrophic microbial denitrification material and preparation and application methods thereof Download PDFInfo
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- C02F3/00—Biological treatment of water, waste water, or sewage
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Abstract
The invention discloses a sulfur-based autotrophic microbial denitrification material and a preparation and application method thereof. The autotrophic nitrogen removal material is used as a filler of an anaerobic biological filter to construct a deep anaerobic biological filter bed, 25mg/L of nitrate and nitrite nitrogen can be reduced to be below 5mg/L at a proper temperature and within 40-60min of hydraulic retention time, and the material can replace organic carbon sources such as sodium acetate and the like to perform denitrification and nitrogen removal, so that the nitrogen removal cost is saved by over 50 percent.
Description
Technical Field
The invention relates to the technical field of environmental functional materials and sewage treatment, in particular to a preparation and application method of an autotrophic microorganism denitrification material.
Background
Nitrogen is one of the most important elements causing eutrophication of water bodies, whereas in the past the focus in water treatment and surface water environments has been primarily on the control of ammonia nitrogen. In recent years, as eutrophication of water bodies becomes more serious, particularly urban black and odorous rivers widely appear, nitrate nitrogen and total nitrogen are brought into pollution discharge and water body control indexes, and increasingly strict nitrogen control standards are established everywhere.
Nitrification-heterotrophic denitrification is always the mainstream process technology for wastewater denitrification, which converts organic nitrogen and ammonia nitrogen in water into nitrate nitrogen through an aerobic process, then returns the sewage to an anoxic tank, and converts the nitrate nitrogen into nitrogen through heterotrophic denitrification microorganisms by using organic matters in the sewage as electron donors. The heterotrophic denitrification technology meets the increasingly strict water quality standard of total nitrogen in the discharged water and also meets certain obstacles: firstly, the total nitrogen can reach the discharge standard only by a very high reflux ratio, which causes excessive energy consumption and uneconomic water treatment; secondly, as the retention time of the wastewater in the septic tank and the drainage pipeline is long, and a microorganism degrades organic matters, part of carbon sources are consumed, so that the carbon source in the wastewater entering a sewage treatment plant is insufficient, the carbon-nitrogen ratio is too low, and the requirement of heterotrophic denitrification on organic carbon cannot be met; thirdly, under the condition of insufficient carbon source, an anaerobic biofilter is commonly added behind a secondary sedimentation tank at present, organic carbon is added for denitrification by heterotrophic denitrifying bacteria, but the addition of sodium acetate and other medicaments causes too high denitrification cost, the adding amount is not controlled in place, and the problem of secondary pollution caused by too high COD (chemical oxygen demand) of the effluent is also caused.
In order to make up for the deficiency of heterotrophic denitrification and adapt to the requirement of advanced denitrification in water treatment, the sulfur autotrophic denitrification technology is rapidly developed as a representative autotrophic denitrification technology in recent years. The sulfur autotrophic denitrification is that facultative anaerobic microorganisms such as thiobacillus denitrificans use inorganic carbon as a carbon source to complete anabolism, and simultaneously, sulfur and reducing sulfur compounds (thiosulfate, sulfite and sulfide) are used as electron donors to reduce nitrate into nitrogen, wherein the sulfur is used as the electron donor for denitrification, which is a main development direction. The sulfur autotrophic denitrification technology is widely concerned by scholars at home and abroad because no additional carbon source is needed, has the advantages of rich and cheap sulfur resources, low sludge production, low treatment cost and the like, and is a hot spot for research in the field of denitrification at present. Sulfur is used as an electron donor to generate water acidification in the autotrophic denitrification process, and carbonate such as limestone is usually used as a medium for stabilizing the pH value of a system. The existing sulfur-limestone autotrophic denitrification system mixes limestone and elemental sulfur particles according to a certain proportion and then uses the mixture as a filler, the filler is filled into a reaction filter column for sewage treatment, and the limestone is continuously dissolved in the treatment process, so that the reduction of pH is buffered. For example: patent CN201910887769.2, a biological retention pool filler based on sulfur autotrophic denitrification, which is to mix sulfur particles and carbonate mineral quartz sand or crushed stone according to a proportion and fill the mixture into a filter pool for autotrophic microbial denitrification. Patent CN202110289081.1, a denitrogenation material based on sulfur autotrophic denitrification, a preparation method and an application thereof, wherein the denitrogenation material is obtained by heating and melting, uniformly mixing, molding, cooling and molding 35-65% of sulfur, 25-50% of carbonate powder, 5-15% of slow-release phosphorus material and 0.5-5% of foaming agent at 115-180 ℃. Patent CN202010863127.1, a novel nitrogen and phosphorus removal sulfur-based composite material and a preparation method thereof, which is obtained by processing a mixture of a sulfur-rich solution, calcined dolomite, gypsum powder and siderite powder. Patent No. cn201910332916.x, a preparation method and application method of a sulfur light material modified by calcium/magnesium carbonate powder material, mixing sulfur and calcium/magnesium carbonate powder, melting at high temperature, foaming the molten mixture under stirring, and cooling and molding the molten mixture to obtain the light material. The existing sulfosulpho-denitrification material only considers the problem of how to neutralize the acid produced by oxidizing sulfur in the denitrification process of autotrophic microorganisms, so that a certain proportion of carbonate minerals are added into the composite material prepared from sulfur and used for sulfur granules, and the pH value of a system for neutralizing the acid produced by oxidizing sulfur is stabilized in a range acceptable by the microorganisms. The prior sulfur autotrophic nitrogen removal material has the following outstanding problems:
(1) the existing sulfur sulfosulphur autotrophic denitrification material has a low denitrification rate, so that a treatment tank occupies too large land area. The sulfur and the microorganisms interact to reduce nitrate nitrogen in a process needing electron transfer, the sulfur belongs to insoluble solid matters, and the electron transfer between sulfur particles and the microorganisms is a key factor for restricting the denitrification reaction speed and is also a root cause of low sulfur autotrophic denitrification speed. Usually, the heterotrophic denitrification anaerobic biofilter added with sodium acetate can stably meet the control requirements of nitrate nitrogen and total nitrogen when the hydraulic retention time is 25-40min, and the hydraulic retention time of the sulfur granule autotrophic denitrification is over 100 min. How to improve the biological reaction speed of the sulfur autotrophic nitrogen removal material through the material preparation method and make the hydraulic retention time of the nitrogen removal reaction reach or approach the hydraulic retention time of the heterotrophic nitrogen removal is a key technical problem which needs to be solved urgently at present.
(2) The process of sulfur autotrophic nitrogen removal is divided into two steps, nitrate is reduced into nitrite, nitrite is reduced into nitrogen, and the two steps are respectively completed by different microorganisms. The sulfur autotrophic denitrification microorganisms are very sensitive to pH value, the optimal pH value is 7-7.5, and the denitrification reaction rate of the microorganisms can be influenced by overhigh and overlow pH values. Due to the difference of metabolic rates of nitrate reducing microorganisms and nitrite reducing microorganisms and the difference of pH sensitivity, nitrite accumulation often occurs in a biofilter constructed by sulfur particles and carbonate particles, so that denitrification efficiency is influenced. How to construct the composition, structure and reactivity of the material and construct a microenvironment which is beneficial to the attachment, increment and metabolism of microorganisms is the key of material preparation.
(3) The sulfur autotrophic nitrogen removal material is generally filled into the anaerobic nitrogen removal filter tank as particles, and the key to how to prevent the filler from being blocked is the operation of water treatment. The existing denitrification biological filter adopts regular back flushing to solve the problem of blockage. However, the backwashing process not only washes out the particles causing the blockage, but also causes the falling of the biological membrane, and the recovery of the biological membrane requires a certain time period, thereby influencing the effluent quality in the recovery stage of the biological membrane. In addition, the sulfur particles have low density and low strength, and have large difference with the density and the strength of carbonate minerals, so the back washing easily causes the abrasion, the increase and the loss of the sulfur particles, and the separation of the sulfur particles and the carbonate particles.
Disclosure of Invention
Through a large number of static and dynamic denitrification experimental researches, the invention provides a sulfur-based autotrophic microbial denitrification material and a preparation and application method thereof, so as to solve the problems in the prior art and provide materials and technical support for the application of sulfur autotrophic denitrification in the field of sewage treatment.
The technical scheme adopted by the invention is as follows:
a sulfur-based autotrophic microorganism denitrification material is characterized in that: the sulfur-based autotrophic microbial denitrification material is a particulate matter obtained by mixing a sulfur-containing raw material and lime powder, and then melting, forming and surface carbonating the mixture. In the sulfur-based autotrophic microbial denitrification material, the mass percent of sulfur is not less than 70%, the mass percent of lime is not less than 10%, and a small amount of calcium carbonate, iron compounds and organic compounds are also contained.
The preparation method of the sulfosulfo autotrophic microorganism denitrification material comprises the following steps:
step 1, uniformly mixing a sulfur-containing raw material and lime powder according to a dry-basis mass ratio of 3-9: 1 to obtain a mixed material;
step 2, adding the mixed material into a hopper of a forming machine, heating to 125-140 ℃ to melt sulfur, and enabling the mixed material to be in a viscous plastic flowing state; then, extruding the material by a forming machine, cutting and cooling to obtain spherical or rod-shaped particles with the diameter of 2-50 mm;
or: heating and melting the mixed material, cooling the mixed material into a block, and crushing the block into particles with the particle size of 2-50 mm;
step 3, spraying water on the surface of the particles obtained in the step 2, and introducing CO2Of the gas of (2) to make the particlesThe calcium oxide on the surface is hydrated into calcium hydroxide and then carbonated into calcium carbonate, and finally the pH value of the particle soaking water solution is not more than 10, so that the sulfosulfo autotrophic microorganism denitrification material is obtained.
The phase composition of the sulfur-based autotrophic microbial denitrification material obtained by the invention comprises elemental sulfur, calcium hydroxide, calcium oxide, calcite, a small amount of iron-manganese compound and organic matter; the bulk density of the sulfur-based autotrophic microbial denitrification material is 0.8-1.3 g/cm3The bulk porosity is 40-60%.
The application method of the sulfosulfo autotrophic microorganism denitrification material comprises the following steps:
(1) uniformly mixing the sulfur-based autotrophic microbial nitrogen removal material with limestone particles or dolomite particles with the same particle size according to a mass ratio of 1-2: 1 to obtain a biological filter filler; uniformly filling the filler into a biological filter for sewage treatment;
(2) introducing nitrate-containing wastewater to be treated into the biological filter, and inoculating the wastewater to the concentration>2*107cfu/mL of thiobacillus denitrificans anaerobic microorganism bacterial liquid, wherein the volume of the added bacterial liquid is 0.1-1% of the volume of the water in the tank;
(3) driving pool water to circulate for 2-6 hours according to hydraulic retention time by a pump, and promoting anaerobic denitrification microorganisms to form a film on the surface of the filler at the water temperature of more than 15 ℃; when the denitrification efficiency reaches more than 80 percent, the microorganism film is mature and starts to operate normally;
(4) when the biological filter operates normally, the hydraulic retention time parameter value of the biological filter is 40-60min according to the requirements of water inlet and water discharge on nitrate nitrogen and total nitrogen.
Furthermore, the effective thickness of the packing layer is designed to be larger than 2m in practical engineering application so as to ensure that the flow velocity of gaps in the packing layer meets the requirement.
Further, along with the consumption of sulfogroup autotrophic microorganism denitrification materials, limestone or dolomite particles in the biological filter, the height of the packing layer is gradually reduced, and when the height of the packing layer is reduced to be more than 10cm, the packing in the step (1) is added to the biological filter.
Compared with the prior art, the invention has the beneficial effects that:
(1) after the sulfur and the lime are compounded, the surface is carbonated, and the large-particle core-shell structure material with alkalinity gradient is constructed. The material prepared by melting and carbonating the sulfur and the lime is adjustable in particle size and high in particle strength, calcium hydroxide and calcium oxide exist in particles, strong basicity exists in the particles, and the particle surface is kept neutral due to carbonating. The strong basicity in the particles enhances the formation of polysulfide species and the release of sulfur dissolved into water, and improves the accessibility and the electron transfer efficiency of the sulfur in the denitrification process of autotrophic microorganisms, so that the speed of the thiobacillus denitrificans for reducing nitrate nitrogen and nitrite nitrogen by utilizing the sulfur can be greatly improved. In the biological filter, calcium hydroxide and calcium oxide exposed on the surface of the denitrification material particles due to reaction act with carbonate ions in water, so that a thin calcite layer always exists, and a filler system is ensured to maintain a long-term stable pH value condition favorable for microbial metabolic denitrification in the water treatment process.
(2) The sulfur and the lime are fused and compounded, so that the mechanical strength of the particles is improved, the particle material with the strength far higher than that of the pure sulfur particles and the sulfur tablets is obtained, and the strength requirement of the water treatment filler is met. Moreover, high-strength granular materials are formed by means of sintering of sulfur and carbonation of lime, and the biological reactivity is improved due to melt compounding. The composition of the sulfur and the lime powder on the micron scale is beneficial to maintaining a pH microenvironment which is beneficial to the proliferation and the metabolism of the thiobacillus denitrificans on the micro scale, and a microenvironment which is more suitable for the attachment growth and the metabolic denitrification of the denitrified microorganisms is formed. Compared with sulfur particles and a composite material of the sulfur particles and carbonate, the material provided by the invention has the advantage that the denitrification reaction rate is greatly improved.
(3) Solves the problem of blockage of the packing layer of the biological filter and saves frequent back washing and negative effects thereof. The main components of the material of the invention are elemental sulfur, calcium hydroxide, calcium oxide and calcite, the minerals are all biological reaction active components in the denitrification process of sulfur autotrophic microorganisms, and SO is generated by redox reaction and neutralization reaction4 2-、Ca2+Dissolved in the denitrification processAnd then lost in water. The content of acid insoluble substances in the selected lime and carbonate particulate material is required to be less than 2%, so that the risk of filter bed layer blockage caused by accumulation of insoluble solid particulate matters is reduced. The prepared autotrophic denitrification material has coarse (2-50mm) particles and large inter-particle gaps, and fine particles are dissolved and disappear preferentially due to the dissolution kinetic effect, so that the inter-particle gaps of the bed layer are regenerated continuously. In engineering application, the depth of an autotrophic denitrification biological bed layer is more than 2m, the hydraulic retention time is less than 40min, and the inter-particle flow velocity is more than 5cm/min, so that the accumulation of suspended matters in particle gaps is eliminated, the blockage of a denitrification filter bed is avoided, and the negative problems caused by back washing and back washing are avoided. Experimental research shows that the sulfur-based autotrophic microbial denitrification material is suitable for the attached growth of heterotrophic bacteria and sulfate-reducing bacteria, and aged and dead microbial residues can be degraded and utilized by sulfate-reducing and other microorganisms in the biochemical reaction process of a biological membrane mainly comprising thiobacillus to form hydrogen sulfide which can be utilized by autotrophic denitrification microorganisms. This process avoids the accumulation of aged biofilm and also prevents plugging of the packing layers. When the dynamic experimental column constructed by the material provided by the invention runs for 1 year, the effluent flow rate is not obviously changed, which indicates that the blockage phenomenon cannot occur.
(4) The proper proportion and the structure of the material components are optimized, the pH value of a stable system is in the most suitable range, and the biological denitrification rate is improved. By utilizing the characteristics that dolomite and limestone have different acid reaction activities and balanced pH values and according to different water qualities needing denitrification treatment, the sulfur-based autotrophic microbial denitrification material is properly selected to be matched with the limestone or the dolomite, the matching ratio of the autotrophic denitrification composite material to the limestone or the dolomite is adjusted, and the pH value of the system is controlled to be stable in the range which is most suitable for the proliferation and metabolism of the thiobacillus denitrificans for a long time. For wastewater with high nitrate nitrogen and low COD, the acid production rate of sulfur oxide is high in the denitrification process of autotrophic microorganisms, and the limestone with high neutralization reaction rate is selected to be matched with the wastewater. For the wastewater with low nitrate nitrogen and higher COD, part of the nitrate is heterotrophically denitrified and generates corresponding alkali, the acid production rate of sulfur is reduced by autotrophic microorganism denitrogenation oxidation, the amount of carbonate consumed by neutralization is correspondingly reduced, dolomite minerals with low neutralization reaction rate are selected to be matched with the nitrate minerals, and the proportion of the sulfur lime composite material and the dolomite is properly improved when the nitrate is filled in a filter tank.
Detailed Description
The following examples are given for the detailed implementation and the specific operation procedures, but the scope of the present invention is not limited to the following examples.
The following examples used the following starting materials:
purchasing 25kg of industrial sulfur, wherein the purity is higher than 95 percent, and the industrial sulfur does not contain toxic and harmful substances; 25kg of industrial lime, wherein the acid insoluble substances in the lime are less than 5 percent. Collecting 25kg of limestone for metallurgy, crushing and screening to obtain particles of 3-6mm, wherein the acid insoluble substance of the limestone is less than 5%. Collecting 25kg of dolomite for fusing agent, crushing and screening to obtain particles of 3-6mm, wherein the acid insoluble substance of dolomite is less than 2%.
Example 1
Uniformly mixing sulfur and lime powder according to a dry basis mass ratio of 8:1 to obtain a mixed material; adding the mixed material into a hopper of a forming machine, heating the mixed material in the forming machine to 125-140 ℃ to melt sulfur, and enabling the mixed material to be in a viscous plastic flowing state; then, the material was extruded through a molding machine, cut and cooled to obtain pellets having a diameter of 5mm and a length of about 10 mm. And (3) putting the formed particles into a tray, spraying water to keep a continuous wetting state, naturally carbonating in the air for 20 days, and detecting that the pH value of the particle soaking water solution is 6.8 to meet the requirement to obtain the sulfur-based autotrophic microbial denitrification material.
Uniformly mixing the prepared sulfur-based autotrophic microbial nitrogen removal material with limestone particles with the particle size of 3-6mm according to a mass ratio of 1:1, and filling the mixture into a dynamic column with the inner diameter of 10cm and the effective height of 50 cm; preparing 1L of simulated wastewater with nitrate nitrogen concentration of 100mg/L, TOC10mg/L by using tap water, blowing nitrogen to remove dissolved oxygen for 10min, and adding directionally enriched thiobacillus denitrificans bacterial liquid (bacterial liquid concentration)>2*107cfu/mL)50 mL; driving water in the column to circulate according to 6h of hydraulic retention time by a peristaltic pump to promote anaerobic denitrification microorganisms to form a film on the surface of the filler; after the denitrification efficiency is detected to reach more than 80 percentAnd the biofilm formation of the microorganisms is mature. Then, a long-term dynamic test is carried out by using simulated wastewater with the prepared nitrate concentration of 25mg/L, TOC10mg/L, and the nitrogen concentration of the nitrate in the effluent water with the water temperature of more than 15 ℃ is less than 5mg/L and far lower than the wastewater discharge standard.
Example 2
Uniformly mixing sulfur and lime powder according to a dry basis mass ratio of 7:1 to obtain a mixed material; adding the mixed material into a hopper of a forming machine, heating the mixed material in the forming machine to 130-140 ℃ to melt sulfur, and enabling the mixed material to be in a viscous plastic flowing state; then, the material was extruded through a molding machine, cut and cooled to obtain pellets having a diameter of 5mm and a length of about 10 mm. And (3) putting the formed particles into a tray, spraying water to keep a continuous wetting state, naturally carbonating in the air for 20 days, and detecting that the pH value of the particle soaking water solution is 6.8 to meet the requirement to obtain the sulfur-based autotrophic microbial denitrification material.
Uniformly mixing the prepared sulfur-based autotrophic microbial denitrification material with dolomite particles with the particle size of 3-6mm according to the mass ratio of 2:1, and filling the mixture into a dynamic column with the inner diameter of 10cm and the effective height of 50 cm; preparing 1L of simulated wastewater with nitrate nitrogen concentration of 100mg/L, TOC10mg/L by using tap water, blowing nitrogen to remove dissolved oxygen for 10min, and adding directionally enriched thiobacillus denitrificans bacterial liquid (bacterial liquid concentration)>2*107cfu/mL)50 mL; driving water in the column to circulate according to the hydraulic retention time of 6 hours by a peristaltic pump to promote anaerobic denitrification microorganisms to form a film on the surface of the filler; after the denitrification efficiency is detected to reach more than 80%, the biofilm formation of the microorganisms is mature; and then, carrying out a long-term dynamic test on the simulated wastewater with the prepared nitrate concentration of 15mg/L, TOC-20 mg/L, wherein the nitrate nitrogen concentration of the effluent water with the water temperature of more than 15 ℃ is less than 4mg/L and is far lower than the wastewater discharge standard.
The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent alterations and modifications are intended to be included within the scope of the present invention, without departing from the spirit and scope of the invention.
Claims (6)
1. A sulfur-based autotrophic microorganism denitrification material is characterized in that: the sulfur-based autotrophic microbial denitrification material is a particulate matter obtained by mixing a sulfur-containing raw material and lime powder, and then melting, forming and surface carbonating the mixture.
2. The sulfur-based autotrophic microbial nitrogen removal material according to claim 1, wherein: in the sulfur-based autotrophic microbial denitrification material, the mass percent of sulfur is not less than 70%, and the mass percent of lime is not less than 10%.
3. A method for preparing the sulfur-based autotrophic microbial nitrogen removal material according to claim 1 or 2, comprising the steps of:
step 1, uniformly mixing a sulfur-containing raw material and lime powder according to a dry-basis mass ratio of 3-9: 1 to obtain a mixed material;
step 2, adding the mixed material into a hopper of a forming machine, heating to 125-140 ℃ to melt sulfur, and enabling the mixed material to be in a viscous plastic flowing state; then, extruding the material by a forming machine, cutting and cooling to obtain spherical or rod-shaped particles with the diameter of 2-50 mm;
or: heating and melting the mixed material, cooling the mixed material into a block, and crushing the block into particles with the particle size of 2-50 mm;
step 3, spraying water on the surface of the particles obtained in the step 2, and introducing CO2The calcium oxide on the surface of the particles is hydrated into calcium hydroxide and then carbonated into calcium carbonate, and finally the pH value of the particle soaking water solution is not more than 10, so that the sulfogroup autotrophic microorganism denitrification material is obtained.
4. The method for applying the sulfur-based autotrophic microbial nitrogen removal material according to claim 1 or 2, comprising the steps of:
(1) uniformly mixing the sulfur-based autotrophic microbial nitrogen removal material with limestone particles or dolomite particles with the same particle size according to a mass ratio of 1-2: 1 to obtain a biological filter filler; uniformly filling the filler into a biological filter for sewage treatment;
(2) introducing nitrate-containing wastewater to be treated into the biological filter, and inoculating the wastewater to the concentration>2*107cfu/mL of thiobacillus denitrificans anaerobic microorganism bacterial liquid, wherein the volume of the added bacterial liquid is 0.1-1% of the volume of the water in the tank;
(3) driving pool water to circulate for 2-6 hours according to hydraulic retention time by a pump, and promoting anaerobic denitrification microorganisms to form a film on the surface of the filler at the water temperature of more than 15 ℃; when the denitrification efficiency reaches more than 80 percent, the microorganism film is mature and starts to operate normally;
(4) when the biological filter operates normally, the hydraulic retention time parameter value of the biological filter is 40-60min according to the requirements of water inlet and water discharge on nitrate nitrogen and total nitrogen.
5. The method of application according to claim 4, characterized in that: in practical engineering application, the effective thickness of the packing layer is designed to be more than 2m so as to ensure that the flow velocity of gaps in the packing layer meets the requirement.
6. The method of application according to claim 4, characterized in that: along with the consumption of sulfogroup autotrophic microorganism denitrification materials, limestone or dolomite particles in the biological filter, the height of the packing layer is gradually reduced, and when the height of the packing layer is reduced to be more than 10cm, the packing in the step (1) is added to the biological filter.
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