CN118271121A - Phosphorus recovery method for municipal sludge independent incineration - Google Patents
Phosphorus recovery method for municipal sludge independent incineration Download PDFInfo
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- CN118271121A CN118271121A CN202410378738.5A CN202410378738A CN118271121A CN 118271121 A CN118271121 A CN 118271121A CN 202410378738 A CN202410378738 A CN 202410378738A CN 118271121 A CN118271121 A CN 118271121A
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- incineration
- sludge
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- ash
- phosphorus
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- 239000010802 sludge Substances 0.000 title claims abstract description 85
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000011574 phosphorus Substances 0.000 title claims abstract description 60
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 50
- 238000011084 recovery Methods 0.000 title claims abstract description 40
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000010456 wollastonite Substances 0.000 claims abstract description 44
- 229910052882 wollastonite Inorganic materials 0.000 claims abstract description 44
- 239000000292 calcium oxide Substances 0.000 claims abstract description 34
- 235000012255 calcium oxide Nutrition 0.000 claims abstract description 34
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 14
- 239000013081 microcrystal Substances 0.000 claims abstract description 13
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 10
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000001110 calcium chloride Substances 0.000 claims abstract description 5
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 44
- 239000000377 silicon dioxide Substances 0.000 abstract description 22
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 22
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 17
- 239000011701 zinc Substances 0.000 abstract description 17
- 229910052725 zinc Inorganic materials 0.000 abstract description 17
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 abstract description 8
- 239000004110 Zinc silicate Substances 0.000 abstract description 7
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 abstract description 7
- 239000011787 zinc oxide Substances 0.000 abstract description 7
- 235000019352 zinc silicate Nutrition 0.000 abstract description 7
- 239000003337 fertilizer Substances 0.000 abstract description 4
- 239000011592 zinc chloride Substances 0.000 abstract description 3
- 235000005074 zinc chloride Nutrition 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 abstract 1
- 235000011941 Tilia x europaea Nutrition 0.000 abstract 1
- 239000011575 calcium Substances 0.000 abstract 1
- 229910052791 calcium Inorganic materials 0.000 abstract 1
- 230000008020 evaporation Effects 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 239000004571 lime Substances 0.000 abstract 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 13
- 238000001816 cooling Methods 0.000 description 9
- 229910001385 heavy metal Inorganic materials 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000010865 sewage Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229910001510 metal chloride Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010801 sewage sludge Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000007704 wet chemistry method Methods 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- QPILZZVXGUNELN-UHFFFAOYSA-M sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonate;hydron Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S([O-])(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B13/00—Fertilisers produced by pyrogenic processes from phosphatic materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/24—Alkaline-earth metal silicates
-
- C—CHEMISTRY; METALLURGY
- 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
- C02F11/10—Treatment of sludge; Devices therefor by pyrolysis
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/001—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals for sludges or waste products from water treatment installations
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/12—Sludge, slurries or mixtures of liquids
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/40—Valorisation of by-products of wastewater, sewage or sludge processing
Landscapes
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Fertilizers (AREA)
Abstract
The application relates to a phosphorus recovery method for municipal sludge independent incineration, and belongs to the technical field of sludge treatment. The application provides a phosphorus recovery method for municipal sludge independent incineration, which comprises the following steps: 1) Separately incinerating the dried municipal sludge to obtain sludge ash, and preparing the sludge ash into sludge particles; 2) Adding magnesium chloride and/or calcium chloride into the obtained sludge particles, and performing heat treatment at a high temperature of not lower than 1000 ℃ to obtain a phosphorus recovery product; in step 1), calcium lime and wollastonite microcrystals are added during the separate incineration. In the method, when sludge is incinerated, quicklime and wollastonite microcrystals are added, silicon dioxide in ash reacts with the quicklime to generate wollastonite, so that zinc silicate is prevented from being formed by the reaction of the silicon dioxide and zinc oxide, zinc is removed by evaporation through zinc chloride formation in high-temperature heat treatment, zinc element in a phosphorus recovery product is effectively reduced, and the phosphorus recovery product can be directly used as a plant phosphorus fertilizer.
Description
Technical Field
The application relates to a phosphorus recovery method for municipal sludge independent incineration, and belongs to the technical field of sludge treatment.
Background
With the rapid development of economy and the improvement of town level, the sewage generation and treatment amount are increasing. The sludge is used as a process product of sewage treatment, 30% -50% of pollutants in the sewage are concentrated and collected, the sludge has the dual properties of pollution and resources, the safe treatment and recycling of the sludge are all international research hotspots in the field of sewage treatment, and municipal sewage and sludge contain a large amount of phosphorus resources. Wet chemical processes, thermochemical processes, etc. have been developed in the prior art to recover phosphorus from sewage sludge, sludge liquor and sewage sludge ash.
The sludge drying incineration not only can generate heat capable of generating electricity and reduce the volume of sludge, but also can ensure that 90 percent of phosphorus in the inlet water remains in the incineration ash, thus being the best site for phosphorus recovery. However, incineration ash contains more heavy metals, is not suitable for direct return to agriculture, and cannot be directly used as a raw material for fertilizer production. Thus, the key to ash phosphorus recovery is the removal and utilization of heavy metals, as well as the recovery of relatively pure phosphate. Ash phosphorus recovery techniques include biological processes, wet chemical processes, and thermochemical processes. Biological methods rely on microbial activities to extract and purify phosphorus, including bioleaching and biophosphorylation. In the wet chemical method phosphorus recovery, acid or alkali is added to change the environment of ash acid and alkali so as to increase the solubility of phosphorus and transfer the phosphorus from a solid phase to a liquid phase, thereby realizing the extraction of phosphorus; further purifying the phosphorus by chemical extraction or the like. The thermochemical method heats sludge ash in a high-temperature environment to separate heavy metals and compounds thereof in a steam form, thereby realizing gas-solid separation of the ash and the heavy metals; the volatile metals are then recovered during the gas scrubbing process. The thermochemical method can synchronously realize the extraction and the purification of the phosphorus, and is a relatively simple and economic method for recycling the ash content phosphorus.
Examples of the thermochemical processes in the prior art include therapeutics, ash Dec, mephrec, and the like. The Ash content of the sludge can be mixed with environment-compatible chlorides by utilizing the characteristics of low melting point, high volatility, easy water dissolution and the like of the metal chlorides in the Ash Dec process, and chemical reaction is carried out at high temperature, so that heavy metals such as chromium, copper, lead, zinc, tin and the like and chlorine form the metal chlorides with high volatility, and further separation and removal of the metal chlorides and the Ash content are realized; the phosphorus-containing compounds in the residual ash are mostly plant absorbable phosphorus phases or are supplied as raw materials for producing phosphate fertilizer.
In the Ash Dec process, because silicon dioxide exists in Ash, zinc element cannot volatilize in a form of zinc chloride and be removed after zinc oxide reacts with the silicon dioxide to generate zinc silicate salt, so that a phosphorus recovery technology is necessary to be provided, and the problem that zinc cannot be removed well in the process of preparing a phosphorus recovery product by recovering sludge and burning Ash in the Ash Dec process is solved.
Disclosure of Invention
In order to solve the problems, the method is provided, wherein quick lime and wollastonite microcrystals are added during sludge incineration, silicon dioxide in ash reacts with the quick lime to generate wollastonite, zinc silicate is prevented from being formed by the reaction of the silicon dioxide and zinc oxide, zinc metal element in a phosphorus recovery product is prevented from being excessively remained because the zinc silicate is difficult to remove, and zinc silicate is prevented from being formed by adding the quick lime, so that zinc metal element can be formed into zinc chloride and evaporated to be removed in high-temperature heat treatment, and finally, zinc element in the phosphorus recovery product can be effectively reduced, so that the phosphorus recovery product can be directly used as a plant phosphorus fertilizer.
According to one aspect of the present application, there is provided a phosphorus recovery method for municipal sludge separate incineration, the method comprising the steps of:
1) Separately incinerating the dried municipal sludge to obtain sludge ash, wherein the sludge ash is prepared into sludge particles;
2) Adding magnesium chloride and/or calcium chloride into the obtained sludge particles, and performing heat treatment at a high temperature of not lower than 1000 ℃ to obtain a phosphorus recovery product;
and in the step 1), quicklime and wollastonite microcrystals are added during the independent incineration.
The quick lime and wollastonite microcrystal are added into municipal sludge and then are directly burnt, the quick lime can react with silicon dioxide in the municipal sludge to form wollastonite, so that the silicon dioxide is fixed in a form of wollastonite, the form that the silicon dioxide reacts with zinc oxide to form zinc silicate which is difficult to remove through an Ash Dec process is avoided, zinc metal can be evaporated and removed through a zinc chloride form through the Ash Dec process, the added wollastonite microcrystal can become a carrier for adhering to the generated wollastonite component, and the existence of the wollastonite microcrystal can promote the calcium oxide to react with the silicon dioxide to form the wollastonite component, so that the silicon dioxide component in the municipal sludge is effectively fixed, and the subsequent removal of zinc metal element is facilitated.
Alternatively, sodium carbonate or sodium hydroxide is also added during the separate incineration in the step 1), and experimenters find that the direct incineration of municipal sludge by adding sodium carbonate or sodium hydroxide can promote the formation of wollastonite components from calcium oxide and silicon dioxide.
Optionally, the conditions of the separate incineration include:
The first incineration stage has a temperature of 900-1100 ℃ for 15-25 h, the second incineration stage has a temperature of 1300-1500 ℃ for 5-10 h, the third incineration stage has a temperature of 800-900 ℃ for 2-5 h, the fourth incineration stage has a temperature of 1000-1200 ℃ for 15-25 h.
Optionally, in the condition of separate incineration, the cooling rate from the second incineration stage to the third incineration stage is not lower than 80 ℃/h.
Optionally, in the condition of single incineration, the cooling rate from the second incineration stage to the third incineration stage is 100-200 ℃/h.
The experimenter finds that the specific cooling condition can obviously promote the calcium oxide and silicon dioxide to form wollastonite components, a third burning stage is arranged in the direct burning process, the temperature condition of the stage is suitable for combining the newly generated wollastonite components with the added wollastonite microcrystalline outer layer, if the temperature of the third burning stage is too low, the heat movement capability of the newly generated wollastonite components is weak and is difficult to effectively adsorb on the wollastonite microcrystalline outer layer, and if the temperature of the third burning stage is too high, the heat movement capability of the newly generated wollastonite components is too strong and is difficult to adsorb and combine on the wollastonite microcrystalline outer layer. And, the experimenter finds that only if the cooling rate of not lower than 80 ℃/h is satisfied and enters the third incineration stage, the newly generated wollastonite component can be effectively adsorbed on the outer layer of the wollastonite microcrystal.
Optionally, the weight of the wollastonite crystallites added is not less than 0.5% by weight of the quicklime added.
Optionally, the ratio of the wollastonite crystallites added to the quicklime added is 1-2% by weight.
Optionally, the ratio of the added sodium carbonate or sodium hydroxide to the added quicklime is 10-30% by weight.
According to another aspect of the application, there is provided the use of any of the above described municipal sludge solely incinerated phosphorus recovery methods in sludge treatment.
Optionally, the sludge treatment mode is to directly incinerate sludge and then recycle phosphorus from Ash obtained by incineration by adopting an Ash Dec process.
The beneficial effects of the application include, but are not limited to:
1. According to the phosphorus recovery method for separately incinerating municipal sludge, when sludge particles are treated by adopting an Ash Dec process, zinc metal ions cannot be effectively removed due to the fact that silicon dioxide reacts with zinc oxide.
2. According to the phosphorus recovery method for separately incinerating municipal sludge, wollastonite microcrystals are added, so that in the direct incineration process, the existence of wollastonite microcrystals can promote the reaction of calcium oxide and silicon dioxide to form wollastonite components, and the generated wollastonite tends to be adhered and combined outside the added wollastonite microcrystals, so that the reaction of calcium oxide and silicon dioxide can be remarkably improved.
3. According to the phosphorus recovery method for separately incinerating municipal sludge, the reaction of calcium oxide and silicon dioxide can be obviously promoted by further adding sodium carbonate or sodium hydroxide, so that the silicon dioxide is fixed in the form of wollastonite, and zinc silicate is not formed by the reaction of the silicon dioxide and zinc oxide, so that the removal of zinc element is not influenced.
4. According to the phosphorus recovery method for separately incinerating municipal sludge, when sludge is directly incinerated, a third incineration stage is added in the incineration process, the temperature is rapidly reduced to the third incineration stage at the cooling rate of not less than 80 ℃/h, the temperature is increased again to enter a fourth incineration stage after 2-5 h, wollastonite components formed by calcium oxide and silicon dioxide can be better adhered and combined on the outer layer of the added wollastonite microcrystal, and the subsequent high-temperature continuous reaction in the fourth incineration stage can obviously improve the reaction of the silicon dioxide and the calcium oxide, so that zinc silicate which is difficult to remove and is formed by zinc oxide and silicon dioxide is reduced.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples, and the raw materials and catalysts in the examples of the present application are commercially available unless otherwise specified.
Example 1
The municipal sludge after pretreatment and drying is directly incinerated to prepare ash, and the preparation conditions of the direct incineration comprise: the temperature of the first incineration stage is 1000 ℃, the duration of 20h, the temperature of the second incineration stage is 1400 ℃, the duration of 8h, the temperature of the third incineration stage is 850 ℃, the duration of 3h, the temperature of the fourth incineration stage is 1100 ℃, and the duration of 20h, wherein the cooling rate from the second incineration stage to the third incineration stage is controlled between 130 ℃ and 150 ℃/h. Wherein a treating agent is added to municipal sludge before the municipal sludge is directly incinerated, specifically, calcium oxide and wollastonite crystallites are added to ash, wherein the weight of the wollastonite crystallites is 1% of the weight of the added quicklime.
And (3) preparing ash obtained after municipal sludge is directly incinerated into sludge particles, adding calcium chloride into the sludge particles for high-temperature heat treatment, wherein the heat treatment temperature is not lower than 1000 ℃, the treatment time is not lower than 10min, and the phosphorus recovery product is obtained after heat treatment.
Example 2
The municipal sludge after pretreatment and drying is directly incinerated to prepare ash, and the preparation conditions of the direct incineration comprise: the temperature of the first incineration stage is 900 ℃, the duration of the second incineration stage is 25h, the temperature of the second incineration stage is 1300 ℃, the duration of the third incineration stage is 10h, the temperature of the third incineration stage is 800 ℃, the duration of the third incineration stage is 5h, the temperature of the fourth incineration stage is 1000 ℃, and the duration of the fourth incineration stage is 25h, wherein the cooling rate from the second incineration stage to the third incineration stage is controlled to be 100-130 ℃/h. Wherein a treating agent is added to municipal sludge before the municipal sludge is directly incinerated, specifically, calcium oxide and wollastonite crystallites are added to ash, wherein the weight of the wollastonite crystallites is 1.5% of the weight of the added quicklime.
And (3) preparing ash obtained after municipal sludge is directly incinerated into sludge particles, adding magnesium chloride into the sludge particles for high-temperature heat treatment, wherein the heat treatment temperature is not lower than 1000 ℃, the treatment time is not lower than 10min, and the phosphorus recovery product is obtained after heat treatment.
Example 3
The municipal sludge after pretreatment and drying is directly incinerated to prepare ash, and the preparation conditions of the direct incineration comprise: the temperature of the first incineration stage is 1100 ℃, the duration of the second incineration stage is 15h, the temperature of the second incineration stage is 1500 ℃, the duration of the third incineration stage is 5h, the temperature of the third incineration stage is 900 ℃, the duration of the third incineration stage is 2h, the temperature of the fourth incineration stage is 1200 ℃, and the duration of the fourth incineration stage is 15h, wherein the cooling rate from the second incineration stage to the third incineration stage is controlled to be 150-200 ℃/h. Wherein a treating agent is added to municipal sludge before the municipal sludge is directly incinerated, specifically, calcium oxide and wollastonite crystallites are added to ash, wherein the weight of the wollastonite crystallites is 2% of the weight of the added quicklime.
And (3) preparing ash obtained after municipal sludge is directly incinerated into sludge particles, adding magnesium chloride and calcium chloride into the sludge particles for high-temperature heat treatment, wherein the heat treatment temperature is not lower than 1000 ℃, the treatment time is not lower than 10min, and obtaining the phosphorus recovery product after heat treatment.
Example 4
This example is essentially identical to example 1 except that sodium carbonate is also added during the separate incineration, the ratio of added sodium carbonate to added quicklime being 30% by weight.
Example 5
This example is essentially identical to example 1 except that sodium hydroxide is also added during the separate incineration, the ratio of added sodium hydroxide to added quicklime being 10% by weight.
Example 6
The conditions of this example are substantially the same as those of example 1, except that the preparation conditions for direct incineration include: the first incineration stage has a temperature of 1000 ℃ and a duration of 20 hours, the second incineration stage has a temperature of 1400 ℃ and a duration of 8 hours, and the third incineration stage has a temperature of 1100 ℃ and a duration of 25 hours.
Example 7
The conditions of this example were substantially the same as those of example 1, except that the cooling rate from the second incineration stage to the third incineration stage was controlled at 50 ℃/h.
Example 8
This example is essentially the same as example 1 except that the weight of the wollastonite crystallites added is not less than 0.1% by weight of the quicklime added.
Comparative example 1
This example is essentially the same as example 1 except that only calcium oxide is added to the ash.
Comparative example 2
The conditions of this example were substantially the same as those of example 1, except that municipal sludge was directly incinerated without adding calcium oxide and wollastonite crystallites to the ash.
Test example 1
The zinc metal in the phosphorus recovery products obtained by treating Ash obtained by directly incinerating municipal sludge and finally removing heavy metal ions by the Ash Dec process in detection examples 1 to 8 was detected, and the results are shown in table 1 below.
TABLE 1 weight percent residual zinc content in phosphorus recovery product
| Test sample | Zinc content (mg/kg) |
| Example 1 | 8.2 |
| Example 2 | 11.0 |
| Example 3 | 9.4 |
| Example 4 | 5.9 |
| Example 5 | 4.9 |
| Example 6 | 24.0 |
| Example 7 | 19.2 |
| Example 8 | 22.6 |
| Comparative example 1 | 83.5 |
| Comparative example 2 | 230.8 |
According to the results shown in Table 1, the phosphorus recovery method for separately incinerating municipal sludge provided by the scheme of the application can effectively reduce the content of heavy metal zinc in the phosphorus recovery product, so that the phosphorus recovery product can be conveniently applied, most of heavy metal elements such as copper, lead, nickel and chromium can be removed after being treated by an Ash Dec process, and residual zinc elements can be further removed by adopting the scheme, and the prepared phosphorus recovery product can be directly applied to plant fertilizers.
In the scheme of the application, municipal sludge is adopted, and can be subjected to precipitation treatment and biological treatment, and meanwhile, in order to directly incinerate the municipal sludge, the municipal sludge is treated by conventional means such as drying and the like. In the scheme of the application, the Ash Dec process is adopted to treat sludge particles prepared by directly incinerating the Ash and to recycle phosphorus, the Ash Dec process is a process well known to a person skilled in the art, and other conditions of direct incineration, such as equipment, can be selected conventionally in the art, such as an incinerator and the like, and the person skilled in the art can select according to the prior art or simple screening as required.
The above description is only an example of the present application, and the scope of the present application is not limited to the specific examples, but is defined by the claims of the present application. Various modifications and variations of the present application will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the technical idea and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A method for recovering phosphorus by separately incinerating municipal sludge, which comprises the following steps:
1) Separately incinerating the dried municipal sludge to obtain sludge ash, wherein the sludge ash is prepared into sludge particles;
2) Adding magnesium chloride and/or calcium chloride into the obtained sludge particles, and performing heat treatment at a high temperature of not lower than 1000 ℃ to obtain a phosphorus recovery product;
and in the step 1), quicklime and wollastonite microcrystals are added during the independent incineration.
2. The method for recovering phosphorus by separately incinerating municipal sludge according to claim 1, wherein sodium carbonate or sodium hydroxide is further added when the separate incineration is performed in the step 1).
3. The phosphorus recovery method for municipal sludge separate incineration according to claim 1, wherein the separate incineration conditions include:
The first incineration stage has a temperature of 900-1100 ℃ for 15-25 h, the second incineration stage has a temperature of 1300-1500 ℃ for 5-10 h, the third incineration stage has a temperature of 800-900 ℃ for 2-5 h, the fourth incineration stage has a temperature of 1000-1200 ℃ for 15-25 h.
4. A phosphorus recovery method according to claim 3, wherein the temperature reduction rate from the second incineration stage to the third incineration stage is not less than 80 ℃/h in the condition of the separate incineration.
5. The method for recovering phosphorus by separately incinerating municipal sludge according to claim 4, wherein the temperature reduction rate from the second incineration stage to the third incineration stage is 100 to 200 ℃/h in the condition of the separate incineration.
6. The method for phosphorus recovery by municipal sludge separate incineration according to claim 1, wherein the weight of the wollastonite crystallites added is not less than 0.5% of the weight of the quicklime added.
7. The method for recovering phosphorus by municipal sludge solely incineration according to claim 6, wherein the ratio of the added wollastonite crystallites to the added quicklime is 1 to 2% by weight.
8. The phosphorus recovery method by municipal sludge solely incineration according to claim 2, wherein the ratio of the added sodium carbonate or sodium hydroxide to the added quicklime is 10 to 30% by weight.
9. Use of the phosphorus recovery method of municipal sludge solely incineration according to any one of claims 1 to 8 in sludge treatment.
10. The use according to claim 9, wherein the sludge treatment is performed by directly incinerating sludge and then recovering phosphorus from Ash obtained by incineration by Ash Dec process.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170113857A (en) * | 2016-03-28 | 2017-10-13 | 한림대학교 산학협력단 | Phosphorus recovery method from sewage sludge ash |
| CN116874162A (en) * | 2023-07-28 | 2023-10-13 | 北控水务(中国)投资有限公司 | Sludge phosphorus recovery method |
| CN117619866A (en) * | 2023-10-26 | 2024-03-01 | 上海市政工程设计研究总院（集团）有限公司 | Phosphorus resource recovery method for sludge incineration fly ash |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170113857A (en) * | 2016-03-28 | 2017-10-13 | 한림대학교 산학협력단 | Phosphorus recovery method from sewage sludge ash |
| CN116874162A (en) * | 2023-07-28 | 2023-10-13 | 北控水务(中国)投资有限公司 | Sludge phosphorus recovery method |
| CN117619866A (en) * | 2023-10-26 | 2024-03-01 | 上海市政工程设计研究总院（集团）有限公司 | Phosphorus resource recovery method for sludge incineration fly ash |
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| Title |
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| QIANG LIU等: "Behavior of fast and slow phosphorus release from sewage sludge–derived biochar amended with CaO", ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH, 23 February 2021 (2021-02-23), pages 28319 - 28328, XP037470502, DOI: 10.1007/s11356-021-12725-z * |
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