CN111253958A - Method for reducing sludge mixed straw pyrolysis resources - Google Patents
Method for reducing sludge mixed straw pyrolysis resources Download PDFInfo
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- CN111253958A CN111253958A CN202010152049.4A CN202010152049A CN111253958A CN 111253958 A CN111253958 A CN 111253958A CN 202010152049 A CN202010152049 A CN 202010152049A CN 111253958 A CN111253958 A CN 111253958A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
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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
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
- C02F11/122—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering using filter presses
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
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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
- C02F2303/00—Specific treatment goals
- C02F2303/06—Sludge reduction, e.g. by lysis
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Treatment Of Sludge (AREA)
Abstract
The invention discloses a method for reducing sludge mixed straw pyrolysis resources, belonging to the field of sludge resource treatment, and the method comprises the following steps: (1) grinding and crushing straw to obtain straw fine powder; (2) mixing the fine straw powder with the excess sludge according to a certain proportion, uniformly stirring, and adding FeCl with a certain concentration into the mixture3Uniformly stirring the solution, and then dehydrating the sludge-straw mixture by using a filter press; (3) drying and granulating the dehydrated mud cakes by using a granulator, and then carrying out pyrolysis on the granules to generate gas; according to the invention, the straw fine powder is mixed into the sludge, the dehydration performance of the sludge is improved, the sludge amount is reduced, the generated dry particles are easy to store and have larger specific surface area, and the pyrolysis process is more sufficient, so that the pyrolysis efficiency is improved, the pyrolysis energy consumption is reduced, and the pyrolysis product is high-purityThe high-cleanness combustible gas can be used as a new energy source to replace non-renewable fossil energy sources.
Description
Technical Field
The invention relates to the field of sewage and sludge recycling, in particular to a method for reducing sludge mixed with straws by pyrolysis and recycling.
Background
With the continuous improvement of the urbanization level of China, the construction of sewage treatment facilities develops at a high speed. In an activated sludge system for municipal sewage treatment, a large amount of activated sludge, i.e., excess sludge, is discharged from a secondary sedimentation tank (or sedimentation zone). By the end of 2019, the total amount of sewage in China reaches 600 hundred million tons, the corresponding sludge production is increased to about 6000 million tons, and the residual sludge is colloidal floc generated in the wastewater treatment process, has complex components, high organic matter content and high water content and contains a large amount of pathogenic bacteria, parasitic ova, heavy metals such as chromium and mercury and other toxic and harmful substances which are difficult to degrade, such as polycyclic aromatic hydrocarbon and the like. The production amount of residual sludge in industrial pollution treatment plants in China is large, most of the residual sludge is treated as dangerous waste (about 2000 yuan/ton), and the operation cost of enterprises is increased.
The floc of the excess sludge has higher high calorific value, and the sludge incineration technology is a treatment mode for reducing and recycling the sludge. The existing sludge incineration technology mainly comprises two types of sludge single incineration and mixed incineration, wherein the mixed incineration is to incinerate the sludge after mixing the sludge with high-calorific-value solid biomass such as coal, straws and the like. Although the incineration can effectively treat the harmful substances in the sludge, the equipment investment and maintenance cost is very high, the energy consumption is overlarge, and the harmful substances such as dioxin, heavy metal particles and the like contained in the flue gas can pollute the environment.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for reducing sludge mixed straw pyrolysis resources, which can improve the dehydration performance of sludge, reduce the discharge amount of sludge, reduce the energy consumption in treatment and pyrolyze the sludge into clean and pollution-free combustible gas.
In order to realize the purpose of the invention, the invention adopts the following technical scheme: a method for reducing sludge mixed straw pyrolysis resources comprises the following steps:
s1, grinding the straws into straw fine powder with the particle size of 50-1000um, mixing the straw fine powder into the residual sludge according to the proportion of 0.05-0.5g/g TSS, wherein the TSS is the dry solid content of the sludge-straw mixture, and uniformly stirring the mixture;
s2, adding FeCl with the concentration of 10-40 wt% into the mixture3Solution of FeCl3The adding amount of the catalyst is 0.1-0.2gFe/gTSS, and after being uniformly stirred, the catalyst is subjected to filter pressing dehydration and dehydrationThe water content of the mud cake is 55-70%;
s3, drying and granulating the dehydrated mud cakes at 40-60 ℃;
s4, putting the dried particles into a pyrolysis furnace, and pyrolyzing at the temperature of 400-800 ℃ in an oxygen-free environment.
The method for reducing the sludge mixed straw resources by pyrolysis is further improved:
preferably, the straw in the step (1) is one or a mixture of two or more of corn, wheat, soybean, peanut, sesame and rice straw.
Preferably, the water content of the excess sludge in the step (1) is 96-99%, and the organic matter content is 65-80%.
Preferably, the filter-pressing dehydration in the step S2 adopts a small plate-and-frame filter press, the pressure of the filter-pressing dehydration is 0.5-1MPa, and the filter-pressing time is 20-40 min.
Preferably, the drying and granulating in the step S3 are performed by using a drying and granulating machine with the rotation speed of 1000-1600 r/min.
Preferably, the granules dried and granulated in the step S3 are cylinders, and have a particle size of 5-10 mm.
Preferably, the pyrolysis environment in step S4 is nitrogen or argon.
Compared with the prior art, the invention has the beneficial effects that:
1) in the invention, a certain proportion of straw fine powder is added into the excess sludge, and FeCl is added3Electrostatic repulsion and hydration among water molecules are overcome through electric neutralization, and then the sludge flocculation structure and the sludge particle size are changed, so that the sludge is destabilized and flocculated and settled, and the subsequent sludge dewatering process is facilitated; in addition, the straw fine powder has certain adsorbability, the content of Extracellular Polymeric Substances (EPS) dissolved out can be reduced, and the straw fine powder also plays a skeleton role in the filter pressing dehydration process, so that more hydrophobic channels are formed in the sludge, the dehydration property of the sludge is improved, and the sludge amount after filter pressing dehydration is greatly reduced.
2) The addition of the straw fine powder in the sludge increases the organic matter content of a sludge system, the specific surface area of the internal structure of the granulation is increased, the prepared granulation is easy to store, and the pyrolysis process is more sufficient, so that the pyrolysis efficiency is improved, and the energy consumption of pyrolysis is greatly reduced.
3) In an oxygen-free environment, the mixed granulation of the sludge and the straws is heated to a certain temperature, and organic matters in the sludge are mainly subjected to thermo-chemical reactions such as thermal cracking of lipids and proteins and are converted into gas, pyrolysis oil, pyrolysis water and carbon residue substances. The invention mixes and granulates sludge and straws for pyrolysis to generate CH4、H2、CO2The clean gas can develop the biomass of the excess sludge, can be compared with the utilization of fossil energy, and finally replaces non-renewable fossil energy to become an important component of a new energy system.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention.
FIG. 1 is a process flow diagram of green treatment for achieving excess sludge reduction and reclamation;
fig. 2 is a structural view of a pyrolysis apparatus used in the present invention.
FIG. 3 is a three-layer EPS composition diagram of excess sludge blended with straw fines at the ratio of 0, 0.2g/gTSS, 0.5g/gTSS, respectively.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below with reference to the accompanying drawings and embodiments, and all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without creative efforts belong to the protection scope of the present invention. Firstly, preparing the following raw materials and reagents:
1. excess sludge: a sewage treatment plant of the Beijing Xiaohe;
2. straw: mixing corn stalks and wheat stalks in a mass ratio of 7:3 in Shandong area;
the main components and the content (%) of each component of the straw were analyzed, and the results were as follows: cellulose-41%, hemicellulose-24%, lignin-28%, extractable component-2%, ash-0.4%.
3、FeCl3: AR grade, produced by national drug group chemical reagents, Inc.;
example 1
1. Crushing straws into fine powder with the particle size of 500 um;
2. respectively placing 6 parts of 300mL of excess sludge in 6 beakers, then respectively mixing straw fine powder in the 6 beakers according to the proportion of 0, 0.05, 0.1, 0.2, 0.4 and 0.5g/g TSS, placing the beakers in the stirring position of a six-connection stirrer, starting a coagulation stirrer, stirring for 30min, and respectively measuring the capillary water absorption time (CST) and the sludge specific resistance of 6 parts of mixture; FeCl with the mass concentration of 30 percent is respectively added into 6 beakers3The solution is stirred evenly and FeCl is added3The adding amount of the mixture is 0.15g Fe/g TSS, the mixture is stirred for 10min, and the capillary water absorption time (CST) and the specific sludge resistance of 6 parts of mixture are respectively measured;
capillary water absorption time (CST) is an index for evaluating the sludge dewatering performance, a Triton304MCST determinator is adopted in an experiment, Whatman 17-grade standard chromatography filter paper is placed in the experiment, 8mL of experimental sludge is taken and poured into an 18mm cylindrical funnel of the determinator, data is recorded after the reading is stable, namely the sludge CST value, and the determination results are shown in the following table 1;
the sludge Specific Resistance (SRF) is the resistance per unit filtration area when the unit mass of sludge is filtered under a certain pressure, and is a comprehensive index of the sludge filtration characteristics. Taking 100mL of a sample to be measured in a measuring cylinder, setting the constant air pressure of a vacuum pump to be 0.06MPa, counting by software to be 10 s/time, stopping suction filtration when a mud cake cracks, and measuring results are shown in the following table 1;
TABLE 1 influence of straw blending on Capillary Suction Time (CST) and sludge specific resistance
As can be seen from Table 1, FeCl is added during coagulant addition3Firstly, the specific resistance and CST of the sludge are gradually reduced along with the increase of the mixing amount of the straw fine powder, and when the sludge is not mixed, the SRF and the CST are respectively 4.1 x 109s2G and 399s, when the mixing amount of the straw fine powder is 0.5g/gTSS, the SRF and the CST respectively decrease to 3.63 x 109s2G and 32.6 s. FeCl coagulant is added3And then, the SRF and CST of the sludge are greatly reduced, and the SRF and CST are further reduced along with the increase of the mixing amount of the straw fine powder, so that the straw fine powder of the straw powder has certain adsorbability, and the straw fine powder also plays a role of a skeleton in the filter pressing dehydration process, so that more hydrophobic channels are arranged in the sludge, and the dehydration property of the sludge is further improved.
Example 2
1. Crushing straws into fine powder with the particle size of 500 um;
2. respectively placing 3 parts of 300mL of excess sludge in 3 beakers, then respectively mixing straw fine powder in the 3 beakers according to the proportion of 0 g/gTSS, 0.2g/gTSS, placing the beakers in the stirring position of a combined stirrer, starting the coagulation stirrer, stirring for 30min, and respectively taking 50mL of each of the 3 parts of mixture for measuring Extracellular Polymers (EPS);
measuring the EPS components and the filtrate components of the sludge by using a HitachiF-7000 type three-dimensional fluorescence spectrometer; the excitation light source is a xenon arc lamp with an excitation wavelength lambda Ex200 nm-400 nm, and emission wavelength lambda Em220 nm-550 nm, excitation and emission slit width of 5nm, and scanning speed of 12000 nm/min. The EPS extraction reference Cao Bidi et al experiment method comprises the following steps: centrifuging the reserved 3 parts of 50ml solution to be detected at 3000rpm for 5min, and taking supernatant for measuring S-EPS; removing supernatant, adding 0.05% NaCl solution until the volume of the original mud sample is uniformly shaken, performing ultrasonic treatment at 20KHZ for 10min, then performing horizontal oscillation at 150rpm for 10min, performing ultrasonic treatment for 2min, centrifuging at 5000rpm for 10min, and taking supernatant for determining LB-EPS; removing supernatant, adding 0.05% NaCl solution, shaking, performing ultrasonic treatment for 3min, heating in 60 deg.C water bath for 30min, centrifuging at 5000rpm for 10min, and collecting supernatant for determining TB-EPS; the results of the measurement of three-layer EPS are shown in FIG. 3.
From the test results of FIG. 3, it can be seen that Peak A (lambda) exists in the spectra of S-EPS and LB-EPS extracted from the raw mudEx/Em280/335nm tryptophan-like protein (TPN), PeakB (lambda)Ex/Em＝225/340nm) -Aromatic Proteins (APN), PeaksC (. lamda.) -Ex/Em330/410nm Humic Acid (HA) and PeakD (. lamda.)Ex/Em275/425nm) -Furrinic Acid (FA) four fluorescence peaks were present. The color change marked in the figure shows that the three-dimensional fluorescence color of the three layers of EPS after the sludge is mixed with the straw fine powder is lightened, which shows that the content of protein substances is reduced after the sludge is mixed with the straw fine powder, and the straw fine powder has certain adsorbability, so that the content of EPS dissolved in the sludge can be reduced. Because the concentration of protein substances existing in S-EPS and LB-EPS has important influence on the dehydration of sludge, the sludge can be doped with straw fine powder to improve the dehydration property of the sludge.
Example 3
1) Crushing straws into fine powder with the particle size of 500 um;
2) respectively placing 6 parts of 300mL of excess sludge in 6 beakers, respectively mixing straw fine powder in the 6 beakers according to the proportion of 0, 0.05, 0.1, 0.2, 0.4 and 0.5g/g TSS, placing the beakers in the stirring position of a six-joint stirrer, starting a coagulation stirrer, and stirring for 30 min; FeCl with the mass concentration of 30 percent is added3The solution is stirred evenly and FeCl is added3The adding amount of (1) is 0.15gFe/gTSS, and stirring is carried out for 10 min; respectively carrying out pressure filtration on 6 parts of the mixture for 30min under the pressure of 0.6MPa to prepare mud cakes, and respectively measuring the water content of the dewatered mud cakes, wherein the results are shown in Table 2;
example 4
1) Crushing straws into fine powder with the particle size of 500 um;
2) respectively placing 6 parts of 300mL of excess sludge in 6 beakers, respectively mixing straw fine powder in the 6 beakers according to the proportion of 0, 0.05, 0.1, 0.2, 0.4 and 0.5g/g TSS, placing the beakers in the stirring position of a six-joint stirrer, starting a coagulation stirrer, and stirring for 30 min; FeCl with the mass concentration of 30 percent is added3The solution is stirred evenly and FeCl is added3The adding amount of (1) is 0.15gFe/gTSS, and stirring is carried out for 10 min; respectively carrying out pressure filtration on 6 parts of the mixture for 30min under the pressure of 0.6MPa to prepare mud cakes;
3) respectively drying and granulating 6 parts of the mud cakes at 50 ℃ by using a granulator, wherein the rotation speed of the drying granulator is 1450r/min, and preparing dried particles with the size of 5-10 mm;
4) 2g of each of the 6 dried granules prepared above was ground and pulverized, and the granulation specific surface area of 6 samples was measured by using a micromeritics sap2020 full-automatic multifunctional gas adsorber, respectively, and the results are shown in table 2;
5) 5g of each of the 6 parts of the dried pellets prepared above was taken out and placed in a pyrolysis furnace for pyrolysis. The pyrolysis device is shown in fig. 2, the main body of the pyrolysis device is a tubular furnace, a serpentine condenser pipe is connected to the back of the tubular furnace to cool gas after pyrolysis, a drying pipe is connected to the tail end of a serpentine condenser port to absorb moisture in the gas, a mass flowmeter is connected to the back of the drying pipe to measure the volume of the gas, nitrogen is introduced into the pyrolysis furnace when pyrolysis starts, so that pyrolysis is carried out in an oxygen-free environment, the temperature of the pyrolysis furnace is 600 ℃, the gas yield of pyrolysis is the volume of the gas obtained by subtracting the introduced nitrogen from the counted volume of the final mass flowmeter, the gas yields of 6 parts of dry granules are counted respectively, and the results are shown in table 2;
6) the composition analysis of 6 parts of the gas generated during pyrolysis of the dried pellets was performed, and the results are shown in table 2.
TABLE 2 influence of the blending amount of straw on the sludge cake dewatering and sludge granulation
From table 2, it can be seen that the water content of the obtained mud cake decreases with the increase of the mixing amount of the straws, which indicates that the dehydration effect of the sludge can be improved by the straw mixed sludge; meanwhile, the specific surface area and the gas production rate of the granulation are increased, and when the mixing amount of the straws is 0.5g/gTSS, the specific surface area of the granulation is 3.8m2The increase in/g to 9.3m2The gas production is increased by 0.25L/gTSS from 0.1L/gTSS, which proves that the addition of the straws increases the specific surface area of granulation and has more combustion sites on one hand, thereby improving the pyrolysis efficiency, and on the other hand, the organic matter content of the sludge is improved, so the mixing amount of the straws is increasedThe pyrolysis efficiency of granulation is improved; the gas generated in the pyrolysis process of 6 parts of dry particles is clean and pollution-free gas, and can be used as clean combustion gas to replace non-renewable fossil energy.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (7)
1. A method for reducing sludge mixed straw resources by pyrolysis is characterized by comprising the following steps:
s1, grinding the straws into straw fine powder with the particle size of 50-1000um, mixing the straw fine powder into the residual sludge according to the proportion of 0.05-0.5g/g TSS, wherein the TSS is the dry solid content of the sludge-straw mixture, and uniformly stirring the mixture;
s2, adding FeCl with the concentration of 10-40 wt% into the mixture3Solution of FeCl3The adding amount of the additive is 0.1-0.2gFe/gTSS, filter pressing dehydration is carried out after uniform stirring, and the water content of the dehydrated mud cake is 55-70%;
s3, drying and granulating the dehydrated mud cakes at 40-60 ℃;
s4, putting the dried particles into a pyrolysis furnace, and pyrolyzing at the temperature of 400-800 ℃ in an oxygen-free environment.
2. The method for resource reduction by pyrolysis of sludge mixed straws according to claim 1, which is characterized in that: the straw in the step (1) is one or a mixture of two or more of corn, wheat, soybean, peanut, sesame and rice straw.
3. The method for resource reduction by pyrolysis of sludge mixed straws according to claim 1, which is characterized in that: in the step (1), the water content of the excess sludge is 96-99%, and the organic matter content is 65-80%.
4. The method for resource reduction through pyrolysis of sludge mixed straws according to claim 1, wherein the filter-pressing dehydration in the step S2 adopts a small plate-and-frame filter press, the pressure of the filter-pressing dehydration is 0.5-1MPa, and the filter-pressing time is 20-40 min.
5. The method for resource reduction by pyrolysis of sludge mixed straws according to claim 1, which is characterized in that: the drying and granulating in the step S3 are carried out by adopting a drying and granulating machine with the rotation speed of 1000-1600 r/min.
6. The method for resource reduction by pyrolysis of sludge mixed straws according to claim 1, which is characterized in that: the dried and granulated particles in the step S3 are cylinders, and the particle size is 5-10 mm.
7. The method for resource reduction by pyrolysis of sludge mixed straws according to claim 1, which is characterized in that: the pyrolysis environment in the step S4 is nitrogen or argon.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115286207A (en) * | 2022-08-17 | 2022-11-04 | 无锡德林海环保科技股份有限公司 | Mud drying method |
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