CN114644985B - Filamentous fungi and method for recycling phosphorus in sludge by using same - Google Patents
Filamentous fungi and method for recycling phosphorus in sludge by using same Download PDFInfo
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/02—Biological treatment
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- C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
- C12N1/14—Fungi; Culture media therefor
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P3/00—Preparation of elements or inorganic compounds except carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
Abstract
The invention belongs to the technical field of sludge recycling, and relates to filamentous fungi and a method for recovering phosphorus in sludge by using the filamentous fungi. Aiming at the technical bottlenecks of long treatment period, unstable effect and low recycling degree caused by the action of most acidophilic bacteria for extracting phosphorus from sludge by a microbiological method in the prior art, the application adopts a filamentous fungus strain Talaromyces trachyspermus OU5, the hypha structure of the filamentous fungus strain Talaromyces trachypermus OU is rich, no nutrient or acid-base medicament is required to be added, and the DOM of the sludge can be directly used as a nutrient for rapid growth. The scheme also provides a method for recovering phosphorus from sludge by filamentous fungi, which comprises the steps of inoculating a bacterial strain OU5 into the sludge, destroying the three-dimensional floc structure of the sludge by using the dual functions of biological disintegration and biological acidification, releasing phosphorus in a sludge solid phase, allowing the phosphorus to enter a liquid phase, further obtaining a phosphate-rich sludge floc, and performing dehydration separation to obtain a phosphorus-rich aqueous solution and a sludge cake. The filamentous fungi recovered sludge phosphorus is efficient and stable, and has high economic and practical applicability.
Description
Technical Field
The invention belongs to the technical field of sludge recycling, and particularly relates to filamentous fungi and a method for recycling phosphorus in sludge by using the same.
Background
Phosphorus is an important nutrient element for maintaining all life on the earth, and belongs to a non-renewable strategic reserve resource. In recent years, with the increasing demand of industrial and agricultural production for phosphorus, the reserve of global phosphorus deposits faces a huge challenge, and the phosphate ores available for mining are about to be exhausted in the future for 50-100 years. The sludge is the waste generated after the urban domestic sewage treatment plant purifies the sewage. Due to the enrichment and concentration of microorganisms on phosphorus in the sewage treatment process, the content of total phosphorus in the sludge can reach 1-5% (if the sludge is incinerated, the content of phosphorus in the produced sludge ash can be more than 10%), and the abundance of phosphorus in low-grade phosphate ore is achieved (2-10%). Thus, the phosphorus-rich sludge can serve as an important supplemental phosphorus source.
At present, the methods for releasing and extracting phosphorus from sludge mainly comprise: based on strong acids or bases (H) 2 SO 4 Oxalic acid or NaOH, etc.) to break the cell wall; a microbiological method based on the redox treatment of acidophilic bacteria (Thiobacillus ferrooxidans, bacillus, etc.). Among them, the microbiological method for obtaining phosphorus from sludge is widely concerned by scholars at home and abroad due to relatively low cost, simple process and environmental friendliness, and is considered to have more engineering application prospects.
For example, yu jin Lee et al, journal of Environmental Management 270 (2020) 110818 published by Recovery of phosphor from microbial water treatment sludge treatment microorganisms, and disclosed that ATCC medium 125 (ATCC 2016) is used as a basic growth medium, thiobacillus acidophilus A. Thiobacillus DSM 9463 is used as an active strain, and 48-57% of phosphorus release rate can be obtained after sludge is treated for 17-27 days under the condition of exogenous supply of 5% of sulfur nutrient; the phenomenon that the buffer transition period and the pH value are increased (the pH value is increased to 6.2-7.5) for 2-3 days in the initial stage of treating the sludge by A.thiooxidans DSM 9463 is also described; in addition, the results of chemical sulphuric acid treatment of sludge with slightly lower phosphorus release rates than a.thiooxidans DSM 9463 were reported.
It can be seen that, from the existing research practice, the method for extracting phosphorus from sludge by using the acidophilic bacteria-dependent microorganism has long treatment period (more than 15 days), low phosphorus release rate (less than 60 percent), and especially, the activity of acidophilic bacteria can be gradually weakened under the working condition of long-term continuous operation. For this reason, it is mainly due to: these acidophilic bacteria belong to the group of inorganic chemoautotrophic bacteria, and the growth rate of most autotrophic bacteria is very slow; acidophilic bacteria are suitable for growing in an acid environment (pH is 1.0-3.0), and inoculated to neutral sludge (pH is usually about 7.0-8.0), and a lag phase suitable for growth is needed; in addition, sludge contains large amounts of Dissolved Organic Matter (DOM) that inhibits the growth of autotrophic bacteria and leads to the inactivation of eosinophilic bacteria.
Disclosure of Invention
1. Technical problem to be solved by the invention
Aiming at the technical problems of long treatment period, unstable effect and low resource degree existing in the process of recycling phosphorus from sludge by using an acidophilic bacteria-based microbiological method in the prior art, the application provides a filamentous fungus strain Talaromyces trachyspermus OU5 which has rich hypha structure and can directly and rapidly grow by taking DOM of the sludge as a nutrient (without adding any nutrient or acid-base medicament). The application also provides a method for recovering phosphorus from sludge by using filamentous fungi, and the whole recovery treatment process is efficient, stable, economical and practical.
2. Technical scheme
In order to achieve the purpose, the technical scheme is as follows:
the filamentous fungus strain OU5 is classified and named Talaromyces trachyspatpermus, is preserved in China general microbiological culture Collection center on 19 th.01 th.2022 th, and has the preservation number of CGMCC No.40049.
Application of filamentous fungi in the field of sludge treatment. The filamentous fungal strain Talaromyces trachyspermus OU5 has the following biological properties: the double effects of biological disintegration and biological acidification are realized, the three-dimensional space floc structure of the sludge is effectively destroyed, and a large amount of phosphorus in the solid phase of the sludge is promoted to be rapidly released to enter the liquid phase.
Further, the filamentous fungi are used for recovering phosphorus in the sludge.
A method for recovering phosphorus in sludge by using filamentous fungi comprises the following steps:
culturing the filamentous fungus Strain OU5 to produce a culture containing 10 7 ～10 8 spore/mL filamentous fungus strain OU5 microbial inoculum;
inoculating the microbial inoculum in the sludge, and performing biological treatment to obtain sludge flocs rich in phosphate;
and dehydrating the deflocculated body to obtain a phosphorus-rich aqueous solution and a sludge cake.
Preferably, mechanical dewatering is used: high-pressure filter pressing for dewatering at 15-20Mpa for 30min or plate-frame filter pressing for dewatering at 1.6Mpa for 30min.
Further, the step of culturing the filamentous fungus strain OU5 uses a PDA growth medium, which is: naNO 3 1.5g/L，K 2 HPO 4 0.5g/L，KCl 0.025g/L，MgSO 4 0.025g/L, 1.5g/L of yeast extract and 35g/L of sucrose.
Preferably, the culture is carried out for 3 to 5 days at the temperature of between 25 and 35 ℃ by shaking and aerobic culture.
Further, the concentration of sludge solid in the sludge is 1-5%; the inoculation amount of the microbial inoculum is 5-25% of the volume ratio.
Preferably, the release amount of phosphorus in the sludge is 80-95%.
Preferably, the aeration stirring is carried out for 3 to 5 days at the temperature of between 25 and 35 ℃; the ventilation is to control the content of dissolved oxygen to be 1-3 mg/L.
Further, the method also comprises the steps of removing aluminum, iron, calcium and magnesium impurity components in the phosphorus-rich water solution, and obtaining ferric phosphate or ferrous phosphate through crystallization.
Further, the step of removing the impurity components of aluminum, iron, calcium and magnesium in the phosphorus-rich aqueous solution uses a cation exchange resin.
Further, in the step of obtaining iron phosphate through crystallization, ferric sulfate is added according to the mass ratio of phosphorus to iron of 1.5.
Preferably, the water bath is carried out for 1h at 70 ℃.
Further, in the step of obtaining ferrous phosphate by crystallization, titanium dioxide is added according to the mass ratio of phosphorus to iron of 1.5.
Preferably, the pH value of the titanium dioxide is 7.0, and the titanium dioxide is mixed for 10min.
Biological material preservation information:
the filamentous fungus strain OU5 is classified and named Talaromyces trchyspatpermus, is preserved in the common microorganism center of China general microbiological culture Collection management Committee (the address: no. 3 of West Lu No. 1 of Beijing Kogyo facing Yang district, institute of microbiology of China academy of sciences) in 2022 in 19.01.19.A collection number is CGMCC No.40049.
3. Advantageous effects
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
(1) The filamentous fungus Talaromyces trachypermus OU5 is nonpathogenic and safe to human and animals, and can directly use DOM of sludge as a nutrient in the biotransformation treatment process without adding any nutrient or acid-base agent. The economical and practical performance is stronger.
(2) The invention relates to a method for recovering phosphorus in sludge by utilizing filamentous fungi, which comprises the steps of culturing a filamentous fungus strain OU5 to prepare a sludge product containing 10 7 ～10 8 Inoculating a microbial inoculum of the spore/mL filamentous fungus strain OU5 into sludge for biotransformation to obtain sludge flocs rich in phosphate, and dehydrating and separating the flocs to obtain a phosphorus-rich aqueous solution and a sludge cake. Compared with the existing acidophilic bacteria redox microbial method, the filamentous fungus Talaromyces trachypermus OU5 adopted by the method destroys the three-dimensional space floc structure of the sludge and promotes phosphorus in the sludge solid phase to be released and enter the liquid phase through the double effects of biological disintegration and biological acidification, and the whole treatment process is more efficient and stable. The phosphorus recovery rate can reach the same level with the chemical method using strong acid and strong base, and is higher than the existing scheme using acidophilic bacteria. Moreover, the sludge treated by the method has stable property, is easy to be subsequently treated and utilized, and finally obtains pure phosphorus productsHigh degree, regular shape and structure and high value.
Drawings
FIG. 1 is a flow chart of the process for efficient recovery of phosphorus from sludge by filamentous fungal bioconversion as in example 1;
FIG. 2 is a graph showing the identification of high purity ferrous phosphate synthesized from phosphorus in sludge bioconverted by filamentous fungi in example 1;
FIG. 3 is a diagram showing the physical and morphological patterns of high purity ferrous phosphate synthesized from phosphorus in sludge biotransformed by filamentous fungi in example 1;
FIG. 4 is a graph showing the release kinetics of phosphorus during the treatment of sludge by the acidophilic bacteria in comparative example 1;
FIG. 5 is a graph showing that the acidophilic bacteria treated sludge in comparative example 1 synthesizes iron phosphate rich in impurities;
FIG. 6 is a graph showing the identification of iron phosphate synthesized by phosphorus in sludge biotransformed by filamentous fungi in example 2;
FIG. 7 is a graph showing the physical structure and morphology of iron phosphate synthesized from phosphorus in sludge from the bioconversion of filamentous fungi in example 2;
FIG. 8 is a diagram showing anhydrous ferric phosphate containing a large amount of impurity components and having an irregular morphology in comparative example 2;
FIG. 9 is a colony morphology of Talaromyces trachyspatmus OU5 on solid plates;
FIG. 10 is a view showing the structure of the hypha of Talaromyces trachyspermus OU 5;
FIG. 11 is a graph showing the growth of Talaromyces trachyspatmus OU5 with sludge DOM as the nutrient.
Detailed Description
The invention is further described with reference to specific examples.
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to fig. 1 to 8, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments; all other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
This example is the extraction of phosphorus and the synthesis of ferrous phosphate from liquid sludge using filamentous fungi.
The sludge sample is collected from residual activated sludge discharged by a domestic sewage treatment plant in a certain town of Nanjing, jiangsu, and the basic properties are shown in Table 1.
TABLE 1 basic Properties of sludge samples
In this embodiment, the flow chart of the treatment of the sludge as shown in fig. 1 includes the following steps:
(1) Preparing an inoculation microbial inoculum: selecting OU5 thallus from the inclined plane, inoculating into PDA growth medium, performing aerobic culture at 25 deg.C under shaking for 3 days to obtain a thallus containing 10 7 spores/mL OU5 inoculum.
(2) Sludge treatment: inoculating OU5 microbial inoculum with 5% volume ratio into sludge slurry sample with 3% solid concentration, ventilating and stirring at 30 deg.C, biologically treating for 3 days, decomposing and acidifying sludge, releasing 82% phosphorus, and allowing to enter liquid phase.
(3) Solid-liquid separation: the sludge was subjected to high pressure filter-pressing dehydration (15mpa, 30min) to obtain a phosphorus-rich aqueous solution and a solid sludge cake. Directly burning the sludge cake; the phosphorus-rich solution is used for synthesizing ferrous phosphate.
(4) Removing impurities and synthesizing ferrous phosphate: removing impurities such as aluminum, iron, calcium, magnesium and the like in the phosphorus-rich water solution by adopting 732 cation exchange resin, adjusting the pH to 7.0, and adding phosphorus: adding titanium dioxide into the mixture according to the mass ratio of iron to the titanium dioxide of 1.5, and mixing for 10min in an oxygen-free manner to obtain high-purity rosette-shaped ferrous phosphate (shown in figures 2 and 3).
Comparative example 1
This comparative example is a control for extraction of phosphorus from sludge and synthesis of ferrous phosphate using acidophilic bacteria (Thiobacillus ferrooxidans A.f and Thiobacillus thiooxidans A.t).
The sample was the same as example 1, and the procedure of this comparative example was as follows:
(1) According to the invention patent: thiobacillus ferrooxidans and a method for removing sludge heavy metal (ZL02112924. X) thereof, and a method for biologically removing chromium in Thiobacillus thiooxidans and tannery sludge (ZL 02137921.1) respectively prepare inoculation inoculants A.f, A.t and A.f + A.t.
(2) Sludge treatment: inoculating A.f, A.t and A.f + A.t bactericides respectively to a sludge slurry sample with the water content of 97 percent according to the volume ratio of 5 percent, and adding corresponding nutrients (10 g/L FeSO) respectively 4 ·7H 2 O;6g/L sulphur), was treated at 30 ℃ with aeration and stirring for 8 days, with about 65% phosphorus release (FIG. 4).
(3) Solid-liquid separation: the sludge was subjected to high-pressure filter-pressing dehydration (15mpa, 30min) to obtain a phosphorus-rich aqueous solution and a solid sludge cake. The sludge cake is firstly subjected to lime neutralization to adjust the pH value to 7.0 and then is incinerated; the phosphorus-rich solution is used for synthesizing ferrous phosphate.
(4) Removing impurities and synthesizing ferrous phosphate: removing impurities such as aluminum, iron, calcium, magnesium and the like in the phosphorus-rich water solution by adopting 732 cation exchange resin, adjusting the pH to 7.0, and adding phosphorus: adding titanium dioxide into the mixture according to the mass ratio of iron to the mixture of 1.5, and mixing for 10min in an oxygen-free manner to obtain ferrous phosphate (shown in figure 5) which contains more impurity components and is irregular in appearance.
Example 2
This example is to extract phosphorus and synthesize iron phosphate from sludge incineration ash by using filamentous fungi.
A sample of incineration ash of sludge was collected from a sludge incineration disposal plant from south of Jiangsu, and the basic properties are shown in Table 2.
TABLE 2 basic Properties of sludge incineration Ash
In this embodiment, a flow chart of the treatment of the sludge incineration ash sample is shown in fig. 1, and the treatment method includes the following steps:
(1) Preparing an inoculation agent: selecting OU5 thallus from the inclined plane, inoculating into PDA growth medium, culturing at 35 deg.C under shaking for 3 days to obtain a culture medium containing 10 8 spores/mL OU5 inoculum.
(2) Sludge treatment: the OU5 microbial inoculum is inoculated into the mortar prepared from the sludge incineration ash with the solid concentration of 5 percent according to the volume ratio of 20 percent, the mixture is ventilated and stirred at the temperature of 35 ℃, the treatment is carried out for 3 days, and 95 percent of phosphorus in the sludge is released to obtain the sludge mortar rich in phosphate.
(3) Solid-liquid separation: and (3) performing filter pressing and dehydration on the sludge plate frame to obtain a phosphorus-rich aqueous solution and sludge slag. The sludge residue can be used for making bricks; the phosphorus-rich solution was used to synthesize iron phosphate.
(4) Removing impurities and synthesizing iron phosphate: removing impurities such as aluminum, iron, calcium, magnesium and the like in the phosphorus-rich aqueous solution by adopting 732 cation exchange resin, adding ferric sulfate according to the mass ratio n (P) of phosphorus to iron, wherein n (Fe) = 1.5.
Comparative example 2
The comparative example is a control of release of phosphorus in sludge incineration ash and synthesis of iron phosphate by using a chemical method of hydrochloric acid and oxalic acid.
The sample was the same as example 2, and the procedure for this comparative example was as follows:
(1) Chemical phosphorus release: 20g of sludge incineration ash sample is taken and put into 1L of hydrochloric acid or oxalic acid solution with the concentration of 0.1mol/L, the shaking is carried out for 12h at the temperature of 35 ℃ and the rotating speed of a shaking table of 180rpm, and the water solution rich in phosphorus and sludge are obtained after filtration. Neutralizing sludge slag with lime and making bricks; the phosphorus-rich solution was used to synthesize iron phosphate.
(2) Removing impurities and synthesizing iron phosphate: 732 cationic resin is used for removing impurity components such as aluminum, iron, calcium, magnesium and the like in the phosphorus-rich solution, ferric sulfate is added according to the ratio n (P) of the amount of phosphorus to iron, n (Fe) = 1.5.
TABLE 3 comparison of the effects of the examples, comparative examples 1 and 2 on the recovery of phosphorus from sludge
As can be seen from the examples and comparative examples, the phosphorus recovery rate in the sewage of the application can reach 75-90%, which is equivalent to the existing chemical acid method and is obviously higher than the scheme adopting acidophilic bacteria. The filamentous fungus strain Talaromyces trachypermus OU5 does not have a lag phase suitable for growth like acidophilic bacteria, and the treatment period can stably run within 3-5 days, which is far better than the acidophilic bacteria scheme for 7-15 days. Although the stabilization time of the filamentous fungus treatment method is longer than that of a chemical acid method, the method has no secondary pollution risk, the treated sludge has stable property and is easy for subsequent treatment, and the finally obtained phosphorus product has high purity, regular shape and structure and high value.
Claims (7)
1. The application of filamentous fungi in the field of sludge treatment is characterized in that:
the filamentous fungi is filamentous fungi strain OU5 which is classified and namedTalaromyces trachyspermusThe strain is preserved in China general microbiological culture Collection center (CGMCC) at 19.01.2022 with the preservation number of CGMCC No. 40049;
and recovering phosphorus in the sludge by using the filamentous fungi.
2. The use of a filamentous fungus according to claim 1 in the field of sludge treatment, wherein: the method comprises the following steps:
cultivating filamentous fungus Strain OU5 to produce a strain containing 10 7 ~10 8 spore/mL filamentous fungus strain OU5 microbial inoculum;
inoculating the microbial inoculum into sludge, and performing biological treatment to obtain sludge floc-removing bodies rich in phosphate;
and dehydrating the deflocculated body to obtain a phosphorus-rich aqueous solution and a sludge cake.
3. Use of a filamentous fungus according to claim 2 in the field of sludge treatment, characterized in that: what is needed isThe above-mentionedThe step of culturing the filamentous fungal strain OU5 uses a PDA growth medium, which is: naNO 3 1.5 g/L，K 2 HPO 4 0.5 g/L，KCl 0.025 g/L，MgSO 4 0.025g/L, yeast extract 1.5g/L, sucrose 35g/L.
4. Use of a filamentous fungus according to claim 2 in the field of sludge treatment, characterized in that: the concentration of sludge solid in the sludge is 1 to 5 percent; the inoculation amount of the microbial inoculum is 5 to 25 percent of the volume ratio.
5. Use of a filamentous fungus according to claim 2 in the field of sludge treatment, characterized in that: and removing impurity components of aluminum, iron, calcium and magnesium in the phosphorus-rich water solution, and obtaining iron phosphate or ferrous phosphate through crystallization.
6. Use of a filamentous fungus according to claim 5 in the field of sludge treatment, wherein: the step of removing the impurity components of aluminum, iron, calcium and magnesium in the phosphorus-rich aqueous solution uses a cation exchange resin.
7. Use of a filamentous fungus according to claim 5 in the field of sludge treatment, wherein: in the step of obtaining the iron phosphate through crystallization, iron sulfate is added according to the mass ratio of phosphorus to iron of 1.5.
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