CN115490411A - Sludge treatment agent and sludge treatment process - Google Patents
Sludge treatment agent and sludge treatment process Download PDFInfo
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- CN115490411A CN115490411A CN202211453805.2A CN202211453805A CN115490411A CN 115490411 A CN115490411 A CN 115490411A CN 202211453805 A CN202211453805 A CN 202211453805A CN 115490411 A CN115490411 A CN 115490411A
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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
- C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
- C02F11/148—Combined use of inorganic and organic substances, being added in the same treatment step
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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
- C02F11/02—Biological treatment
- C02F11/04—Anaerobic treatment; Production of methane by such processes
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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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Abstract
The invention discloses a sludge treatment agent and a sludge treatment process, wherein the sludge treatment process comprises the steps of adding sludge into a centralized treatment point, adding the sludge treatment agent, adding a plate-and-frame filter press for squeezing, entering a disc dryer, drying by a natural gas boiler, adding the sludge into a mixer, adding sawdust biomass into the mixer, stirring and mixing, feeding the mixture into a rod forming machine to form sludge fuel rods, and feeding the sludge fuel rods into a rod bin; adding into an incinerator for pyrolysis and gasification treatment, cooling the generated high-temperature flue gas by a waste heat boiler, treating by a quench tower, a deacidification tower and a bag-type dust remover, and finally discharging by a chimney to reach the standard and collecting slag. Compared with the prior art, the sludge treatment process has higher dehydration rate and gas production rate, can effectively save energy and reduce cost, and is a clean, environment-friendly and sustainable sludge treatment process.
Description
Technical Field
The invention relates to the technical field of sludge treatment, in particular to a sludge treatment agent and a sludge treatment process.
Background
As the amount of sewage treated increases, the amount of sludge treated increases, and thus the problem of sludge treatment is receiving more attention. In view of the above, many researchers have conducted intensive research on recycling of sludge, the related processes and equipment are continuously updated and perfected, and the sludge produced in sewage treatment plants often contains a large amount of organic matters, germs and the like, which also determines the particularity of the treatment process. The selection of the general sludge treatment process is crucial, and once the treatment process is not properly selected, serious pollution is caused. The sludge treatment refers to the whole process of volume reduction, stabilization and harmlessness of sludge, and the main sludge treatment processes comprise sludge concentration, sludge dehydration, sludge digestion, composting, drying and the like. In the prior art, the sludge treatment technology and equipment are backward, the process is not perfect enough, and functional additives are few.
The invention patent CN106746468B discloses a sludge treatment system and a treatment process. The process comprises the steps of firstly, stabilizing the sludge quality of sludge by a sludge concentration tank; then the sludge enters a sludge conditioning tank to carry out sludge wall breaking through adding a conditioning agent; then, the mixture enters a high-pressure mechanical plate-and-frame filter press to be subjected to filter pressing until the water content is 55-60%; then the sludge enters a sludge drying furnace, and after indirect heat exchange is carried out on low-temperature flue gas generated by a sludge carbonization furnace, the dewatered sludge is dried until the water content is below 10%; then the sludge enters a sludge carbonization furnace, and dried sludge is pyrolyzed by high-temperature flue gas generated by a burning hot blast stove to generate biochar and tail gas; tail gas generated by the sludge drying furnace and the sludge carbonization furnace enters a tail gas purification tower for purification and separation, and generated combustible gas and waste oil are incinerated in an incineration hot blast furnace; the biochar is comprehensively utilized. The invention can economically and efficiently treat the sludge of the sewage treatment plant, thereby realizing the comprehensive utilization of the sludge of the sewage treatment plant. However, the sludge treatment system and the sludge treatment process have the defects of insufficient dehydration rate, low gas production rate and high energy consumption.
Disclosure of Invention
In view of the defects of complex sludge treatment process, high energy consumption, insufficient dehydration rate and low gas production rate in the prior art, the invention aims to provide a sludge treatment agent which has higher dehydration rate and gas production rate when being used in the sludge treatment process, can effectively save energy and reduce cost.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
the invention relates to a sludge treatment process, which comprises the following process steps in parts by weight:
step 1, adding 400-600 parts of sludge with the water content of 75-85% into a centralized treatment point, adding 3~8 parts of sludge treatment agent, and mixing to obtain a mixture;
step 2, adding the mixture prepared in the step 1 into a plate and frame filter press, pressing into a dry mixture, wherein the pressing pressure is 1.0-1.5 Mpa, the pressing time is 0.5-2h, then adding into a disc type dryer, the power of the disc type dryer is 150-200KW, the drying time is 2-5h, drying into a sludge mixture by using a natural gas boiler, the power of the natural gas boiler is 12-169w, the rated evaporation capacity is 3-5T/h, the drying temperature is 350-420 ℃, and generated odor is collected by washing and condensation;
step 3, adding the sludge mixture obtained in the step 2 into a mixer, adding 5-15 parts of sawdust biomass into the mixer, stirring and mixing, feeding into a rod forming machine to form sludge fuel rods, and feeding into a rod bin;
and 4, adding the sludge fuel rods prepared in the step 3 into an incinerator for pyrolysis and gasification treatment, cooling the generated high-temperature flue gas by a waste heat boiler, treating the high-temperature flue gas by a quench tower, a deacidification tower and a bag-type dust remover, and finally discharging the high-temperature flue gas after reaching the standard by a chimney to collect slag.
Preferably, the pyrolysis gasification temperature in the step 4 is 700-900 ℃.
Preferably, the bag-type dust collector in the step 4 treats the flue gas by adopting an activated carbon bag surface adsorption mode.
Preferably, the high-temperature steam generated in the step 4 is used for the disc dryer in the step 2.
Preferably, the odor generated in the step 2 is supplied to the pyrolysis gasification incinerator in the step 4 after being washed and condensed.
The sludge treatment agent is prepared by the following method in parts by weight:
s1, adding 1.5 to 3 parts of industrial starch, 1~2 parts of POE powder and 0.2 to 0.5 part of methacryloxy trimethyl ammonium chloride into 20 to 40 parts of water, fully mixing, then introducing nitrogen for 3 to 8 hours at room temperature, wherein the nitrogen flow is 50 to 100L/h, then adding 0.005 to 0.02 part of ammonium persulfate, reacting at 60 to 70 ℃ for 4 to 8 hours, precipitating the reaction product by using 8 to 12 parts of acetone, filtering, separating, and drying in a vacuum oven at 50 to 70 ℃ for 1 to 3 hours to obtain pretreated starch;
s2, grinding 3~4 parts of the biomass turbid mixture into powder with the particle size of less than 0.4-0.8mm as a biomass raw material, drying at 100-120 ℃ for 10-30h, adding 10-20 parts of 1-4 wt% sulfuric acid aqueous solution into the biomass raw material, mixing, pretreating, adding 5-10 parts of 5-10 wt% sodium bisulfite aqueous solution, reacting for 10-30min, adding 2~5 parts of 3-7 wt% 2-naphthol-7-sulfonic acid sodium salt aqueous solution, and stirring and reacting for 1-3h to obtain pretreated biomass;
s3, adding the pretreated starch prepared in the step S1, the pretreated biomass prepared in the step S2, 0.1-0.5 part of magnesium sulfate heptahydrate and 0.1-0.2 part of zeolite into 20-40 parts of 1-3 mol/L hydrochloric acid, adding 0.4-0.6 part of ethylene-octene copolymer, stirring, dropwise adding 0.1-0.3 part of ethyl orthosilicate, stirring at 80-120 ℃ for 20-30h, centrifuging at 10000-14000rpm for 3-8min, collecting solid, drying at 80-120 ℃ overnight to obtain a crystalline material, soaking the crystalline material in 3~8 parts of 1-3 wt% gallium nitrate (III) aqueous solution, stirring at 20-30 ℃ for 10-20h, filtering and separating, and drying at 50-70 ℃ for 8-112h to obtain the sludge treatment agent.
Preferably, the biomass raw material comprises coconut shells, poplar sawdust and corn stalks according to a mass ratio of 0.5 to 2:0.5 to 1: 1~2.
Preferably, the filtration separation is performed by filtering through a screen with 300 to 500 meshes.
Mixing industrial starch with POE powder and methacryloxy trimethyl ammonium chloride, carrying out catalytic reaction by adopting ammonium persulfate, and precipitating to obtain pretreated starch; treating coconut shells, poplar sawdust and corn straws by dilute sulfuric acid, then adding sodium bisulfite and 2-naphthol-7-sodium sulfonate aqueous solution, and stirring to react to obtain pretreated biomass; adding the pretreated starch and pretreated biomass, magnesium sulfate heptahydrate and zeolite into dilute hydrochloric acid, stirring the mixture at a high temperature for reaction by using an ethylene-octene copolymer and ethyl orthosilicate, and sieving and drying the reaction product to obtain the sludge treating agent.
The anaerobic digestion performance of the sludge is obviously improved along with the prolonging of time and the accumulated gas production. The reason for gas production is mainly that carbohydrates, soluble proteins and the like are decomposed by bacteria to generate gas, wherein the pretreated starch grafted by the methacryloxytrimethyl ammonium chloride can influence the spiral structure of the protein in the sludge, promote the formation of a loose protein molecular structure, improve the hydrophobicity of the surface sludge and further improve the dewatering capacity of the sludge. Also can enhance the decomposition of microorganisms. The biomass is added into dilute sulfuric acid, the acid group promotes cellulose expansion by forming a hydrophilic layer on the surface of the cellulose, the cellulose expansion can improve the internal surface area and expose more active substances in the biomass, so that the sodium bisulfite and the 2-naphthol-7-sodium sulfonate have higher reactivity to the biomass, the yield of total sugar in the biomass is improved, the utilization rate of the microorganism to carbohydrate is improved, and the gas yield is increased.
The mineralization of the sludge in the biological treatment process of the sludge treatment plant is insufficient, and the dehydration condition is poor. In this case, it is extremely difficult to reduce the water content to the lower level even by pressure filtration. In the invention, POE powder and methacryloxy trimethyl ammonium chloride are successfully grafted to a starch main chain, the ordered crystal structure of a starch skeleton is damaged, the surface of the starch shows a smooth elliptic three-dimensional structure, and gaps among particles are obvious. This may provide more active sites for sludge flocculation. The water in the sludge after the grafting of the methacryloxy trimethyl ammonium chloride is easy to remove. Mainly related to charge neutralization, adsorption bridging and hydrophobic groups during processing. The POE powder is introduced to provide active sites for positive charges and hydrophobic groups on the surface of the methacryloxy trimethyl ammonium chloride, and the improvement of the sludge dewatering efficiency is facilitated. The water in the sludge can be separated into free water and bound water, wherein the bound water includes capillary water, surface absorbed water and intracellular bound water. Free water is dispersed in sludge particles and is easily removed by gravity concentration, while bound water is hydrated in cells and is difficult to remove. The lower the compressibility of the sludge, the more porous structures are maintained, the deformation of the sludge is suppressed, and the release of the moisture of the sludge from the porous structures is promoted. Coconut shell, poplar sawdust and corn straw are stirred to react with sodium bisulfite and 2-naphthol-7-sodium sulfonate aqueous solution to condition the compression coefficient of sludge, so that a skeleton structure is formed in the sludge dewatering process, the strength of a flocculating constituent is improved, and a water drainage channel is constructed. After the biomass is treated by adding sodium bisulfite and 2-naphthol-7-sulfonic acid sodium salt aqueous solution, a large cavity structure is formed. This shortens the diffusion distance of water molecules, and has the effect of promoting the transfer of pyrolysis vapors. With further introduction of magnesium sulfate heptahydrate and zeolite, the presence of gallium (III) nitrate hydrate provides a suitable acid site and promotes aromatization reactions, acts to reduce mass transfer resistance and reduce surface acidity, and provides suitable active sites. The diffusion structure is retained and the diffusion effect of the water molecules is significantly enhanced. The invention reduces the production cost, and is a clean, environment-friendly and sustainable sludge treatment process.
Compared with the prior art, the invention has the beneficial effects that:
1) Mixing industrial starch with POE powder and methacryloxy trimethyl ammonium chloride, carrying out catalytic reaction by adopting ammonium persulfate, and precipitating to obtain pretreated starch; treating coconut shells, poplar sawdust and corn straws by dilute sulfuric acid, then adding sodium bisulfite and 2-naphthol-7-sodium sulfonate aqueous solution, and stirring to react to obtain pretreated biomass; adding the pretreated starch and pretreated biomass, magnesium sulfate heptahydrate and zeolite into dilute hydrochloric acid, stirring the mixture at a high temperature through an ethylene-octene copolymer and ethyl orthosilicate for reaction, and sieving and drying the reaction product to obtain a sludge treating agent; the sludge treatment agent has higher dehydration rate and gas production rate, and can effectively save energy and reduce cost;
2) The invention adopts a scientific sludge treatment process, solves the problem of difficult dehydration of the sludge treatment process, reduces the treatment cost, reduces the environmental pollution, and is a clean, environment-friendly and sustainable sludge treatment process.
Drawings
FIG. 1 is a flow diagram of a sludge treatment process of the present invention.
Detailed Description
Hereinafter, the technical solution of the present invention will be described in detail by specific examples, but these examples should be explicitly proposed for illustration, but should not be construed as limiting the scope of the present invention.
The parameters of part of the raw materials in the embodiment of the invention are as follows:
industrial starch, industrialised chemical Limited, ningpo;
sawdust biomass, guangzhou yuyi energy science and technology ltd, length: 2~3 cm, diameter: 8MM, calorific value: 3900 to 4800 kilocalories/kg;
POE powder, shanghai gold plastic jade plastic material Limited, the thermoplastic elastomer that adopts ethylene and octene to realize in situ polymerization, the goods number: LV-3H;
methacryloxytrimethyl ammonium chloride, jonan parallel chemical limited, cat # o: 06, CAS:5039-78-1;
sodium bisulfite, department of fortune (shanghai) biotechnology limited, CAS:7631-90-5;
2-Naphthol-7-sulfonic acid sodium salt, soffield chemical Co., ltd., suzhou, cat #: 135-55-7, CAS:135-55-7;
zeolite, lingshou county mineral products limited, cat # goods: 29, silica content: 50 percent;
ethylene octene copolymer, ningbo Fuplastification Limited, cat #: 51659;
gallium (III) nitrate hydrate, shandong delson new materials ltd, particle size: 10 μm, CAS:69365-72-6.
Example 1
A sludge treatment process comprises the following process steps:
step 1, adding 500 tons of sludge with the water content of 80% into a centralized treatment point, adding 5 tons of sludge treatment agent, and mixing to obtain a mixture;
step 2, adding the mixture prepared in the step 1 into a plate-and-frame filter press to be pressed into a dry mixture, wherein the pressing pressure is 1.2Mpa, the pressing time is 1h, then adding the dry mixture into a disc dryer, the power of the disc dryer is 180KW, the drying time is 3h, drying the dry mixture into a sludge mixture by adopting a natural gas boiler, the power of the natural gas boiler is 14.5KW, the rated evaporation capacity is 4T/h, the drying temperature is 380 ℃, and the generated odor is collected by washing, condensation and collection;
step 3, adding the sludge mixture obtained in the step 2 into a mixer, adding 10 tons of sawdust biomass into the mixer, stirring and mixing, feeding into a rod forming machine to form sludge fuel rods, and feeding into a rod bin;
and 4, adding the sludge fuel rods prepared in the step 3 into an incinerator for pyrolysis and gasification treatment, supplying odor collected in the step 2 to the pyrolysis and gasification incinerator for use, controlling the pyrolysis and gasification temperature to be 750 ℃, supplying generated high-temperature steam to the disc type dryer in the step 2, cooling generated high-temperature flue gas by a waste heat boiler, treating the flue gas by a quench tower, a deacidification tower and a bag-type dust remover, treating the flue gas by adopting an activated carbon bag surface adsorption mode by the bag-type dust remover, and finally discharging the flue gas by a chimney to reach the standard and collecting slag.
The sludge treatment agent is prepared by the following method:
s1, adding 2 tons of industrial starch, 1.3 tons of POE powder and 0.4 ton of methacryloxy trimethyl ammonium chloride into 30 tons of water, fully mixing, introducing nitrogen for 5 hours at room temperature, wherein the nitrogen flow is 80L/h, then adding 0.01 ton of ammonium persulfate, reacting for 6 hours at 65 ℃, precipitating a reaction product by using 10kg of acetone, filtering and separating through a 400-mesh screen, and drying for 2 hours in a vacuum oven at 60 ℃ to obtain pretreated starch;
s2, grinding 1 ton of coconut shell, 0.8 ton of poplar sawdust and 1.5 ton of corn straw into powder with the granularity of less than 0.425mm as a biomass raw material, drying at 105 ℃ for 24 hours, adding 15 tons of 3.5wt% sulfuric acid aqueous solution into the biomass raw material, mixing, pretreating, adding 8 tons of 7wt% sodium bisulfite aqueous solution, reacting for 20 minutes, adding 4 tons of 5wt% 2-naphthol-7-sulfonic acid sodium salt aqueous solution, and stirring and reacting for 2 hours to obtain pretreated biomass;
s3, adding the pretreated starch prepared in the step S1, the pretreated biomass prepared in the step S2, 0.3 ton of magnesium sulfate heptahydrate and 0.15 ton of zeolite into 30 tons of hydrochloric acid of 2mol/L, then adding 0.58 ton of ethylene-octene copolymer, dropwise adding 0.2 ton of ethyl orthosilicate, stirring at 100 ℃ for 24 hours, then centrifuging at 12000rpm for 5 minutes, collecting solid, drying at 105 ℃ overnight to obtain a crystalline material, soaking the crystalline material in 5 tons of 2wt% gallium nitrate (III) hydrate aqueous solution, stirring at 25 ℃ for reaction for 14hours, filtering with a 400-mesh screen, and drying at 60 ℃ for 10 hours to obtain the sludge treatment agent.
Example 2
The process steps of a sludge treatment process are basically the same as those of the example 1, and only the differences are that: the preparation methods of the sludge treatment agent are different.
The sludge treatment agent is prepared by the following method:
s1, grinding 1 ton of coconut shell, 0.8 ton of poplar sawdust and 1.5 ton of corn straw into powder with the granularity of less than 0.425mm as a biomass raw material, drying at 105 ℃ for 24 hours, adding 15 tons of 3.5wt% sulfuric acid aqueous solution into the biomass raw material, mixing, pretreating, adding 8 tons of 7wt% sodium bisulfite aqueous solution, reacting for 20 minutes, adding 4 tons of 5wt% 2-naphthol-7-sulfonic acid sodium salt aqueous solution, and stirring and reacting for 2 hours to obtain pretreated biomass;
s2, adding the pretreated biomass prepared in the step S1, 0.3 ton of magnesium sulfate heptahydrate and 0.15 ton of zeolite into 30 tons of hydrochloric acid of 2mol/L, then adding 0.58 ton of ethylene-octene copolymer, dropwise adding 0.2 ton of ethyl orthosilicate, stirring for 24 hours at 100 ℃, then centrifuging for 5 minutes at 12000rpm, collecting solid, drying overnight at 105 ℃ to obtain a crystalline material, soaking the crystalline material into 5 tons of 2wt% gallium (III) nitrate hydrate aqueous solution, stirring and reacting for 14h at 25 ℃, filtering by a 400-mesh screen, and drying for 10 hours at 60 ℃ to obtain the sludge treatment agent.
Example 3
The process steps of a sludge treatment process are basically the same as those of the example 1, and only the differences are that: the preparation methods of the sludge treatment agent are different.
The sludge treatment agent is prepared by adopting the following method:
s1, adding 2 tons of industrial starch, 1.3 tons of POE powder and 0.4 ton of methacryloxy trimethyl ammonium chloride into 30 tons of water, fully mixing, introducing nitrogen for 5 hours at room temperature, wherein the nitrogen flow is 80L/h, then adding 0.01 ton of ammonium persulfate, reacting for 6 hours at 65 ℃, precipitating a reaction product by using 10kg of acetone, filtering and separating through a 400-mesh screen, and drying for 2 hours in a vacuum oven at 60 ℃ to obtain pretreated starch;
s2, adding the pretreated starch prepared in the step S1, 0.3 ton of magnesium sulfate heptahydrate and 0.15 ton of zeolite into 30 tons of hydrochloric acid of 2mol/L, then adding 0.58 ton of ethylene-octene copolymer, dropwise adding 0.2 ton of ethyl orthosilicate, stirring for 24 hours at 100 ℃, then centrifuging for 5 minutes at 12000rpm, collecting solid, drying overnight at 105 ℃ to obtain crystalline material, soaking the crystalline material into 5 tons of aqueous solution of 2wt% gallium (III) nitrate hydrate, stirring and reacting for 14h at 25 ℃, filtering by a 400-mesh screen, and drying for 10 hours at 60 ℃ to obtain the sludge treating agent.
Example 4
The process steps of a sludge treatment process are basically the same as those of the example 1, and only the differences are that: the preparation methods of the sludge treatment agent are different.
The sludge treatment agent is prepared by adopting the following method:
s1, adding 2 tons of industrial starch, 1.3 tons of POE powder and 0.4 ton of methacryloxy trimethyl ammonium chloride into 30 tons of water, fully mixing, introducing nitrogen for 5 hours at room temperature, wherein the nitrogen flow is 80L/h, then adding 0.01 ton of ammonium persulfate, reacting for 6 hours at 65 ℃, precipitating a reaction product by using 10kg of acetone, filtering and separating through a 400-mesh screen, and drying for 2 hours in a vacuum oven at 60 ℃ to obtain pretreated starch;
s2, grinding 1 ton of coconut shell, 0.8 ton of poplar sawdust and 1.5 ton of corn straw into powder with the granularity of less than 0.425mm as a biomass raw material, drying at 105 ℃ for 24 hours, adding 15 tons of 3.5wt% sulfuric acid aqueous solution into the biomass raw material, mixing, pretreating, adding 8 tons of 7wt% sodium bisulfite aqueous solution, reacting for 20 minutes, adding 4 tons of 5wt% 2-naphthol-7-sulfonic acid sodium salt aqueous solution, and stirring and reacting for 2 hours to obtain pretreated biomass;
s3, adding the pretreated starch prepared in the step S1 and the pretreated biomass prepared in the step S2 into 30 tons of 2mol/L hydrochloric acid, then adding 0.58 ton of ethylene-octene copolymer, dropwise adding 0.2 ton of ethyl orthosilicate, stirring at 100 ℃ for 24 hours, then centrifuging at 12000rpm for 5min, collecting solid, drying at 105 ℃ overnight to obtain a crystalline material, soaking the crystalline material in 5 tons of 2wt% gallium (III) nitrate hydrate aqueous solution, stirring at 25 ℃ for reaction for 14h, filtering with a 400-mesh screen, and drying at 60 ℃ for 10 hours to obtain the sludge treatment agent.
Comparative example 1
The process steps of a sludge treatment process are basically the same as those of the example 1, and only the differences are that: the preparation methods of the sludge treatment agent are different.
The sludge treatment agent is prepared by the following method:
grinding 1 ton of coconut shell, 0.8 ton of poplar sawdust and 1.5 ton of corn straw into powder with the granularity of less than 0.425mm as a biomass raw material, adding the biomass raw material, 2 ton of industrial starch, 0.3 ton of magnesium sulfate heptahydrate and 0.15 ton of zeolite into 30 ton of 2mol/L hydrochloric acid, adding 0.58 ton of ethylene octene copolymer, dropwise adding 0.2 ton of ethyl orthosilicate, stirring for 24 hours at 100 ℃, then centrifuging for 5min at 12000rpm, collecting solid, drying at 105 ℃ overnight to obtain a crystalline material, soaking the obtained crystalline material into 5 ton of 2wt% gallium (III) nitrate hydrate aqueous solution, stirring and reacting for 14h at 25 ℃, filtering by a 400-mesh screen, and drying for 10h at 60 ℃ to obtain the sludge treatment agent.
Comparative example 2
The process steps of a sludge treatment process are basically the same as those of the example 1, and only the differences are that: the sludge treatment process does not add a sludge treatment agent in the process steps.
Test example 1
BMP test
The mixture prepared in step 1 was selected for the pyrolysis pretreatment: each of 3 groups of 200mL of the mixture prepared in step 1 was placed in a 250mL conical flask, and pyrolyzed at 120 ℃ for 60min to obtain a pyrolyzed sludge sample. BMP means the amount of organic matter in the sludge which can be converted into first-degree fever in the anaerobic digestion test of the sludge, and is generally used for judging the influence of pretreatment technology on the anaerobic digestion performance of the sludge. Adding 200mL of pyrolysis sludge sample and 100mL of inoculated sludge into a 500mL fermentation tank, adjusting the pH value to 7.0, sealing after purging with nitrogen for 5min, placing in a 35 ℃ water bath shaking table for anaerobic digestion experiment, collecting the generated gas by adopting a drainage and gas collection method, and periodically monitoring the gas production rate. After the culture for 10 days, the volatile suspended solid VSS is measured by a gravimetric method, the gas production is recorded, each group of experiments is tested for three times, and the average value is taken. The test results are shown in Table 1.
Test example 2
Sludge dewatering Performance test
And (3) taking 20kg of the sludge mixture obtained in the step (2), drying the sludge mixture by adopting a 60 ℃ oven until the sludge mixture is completely dried, weighing the sludge mixture, and calculating the water content of the sludge mixture prepared in the step (2). Each group was tested three times and the average was taken and the test results are shown in table 2.
From the results of test example 1 and test example 2, it can be seen that the sludge treated by the modified biomass prepared by the invention has higher gas production and stronger dehydration performance. The main reason may be that the industrial starch is mixed with POE powder and methacryloxy trimethyl ammonium chloride, and ammonium persulfate is adopted for catalytic reaction, and the pre-treated starch is obtained through precipitation; treating coconut shells, poplar sawdust and corn straws by dilute sulfuric acid, then adding sodium bisulfite and 2-naphthol-7-sodium sulfonate aqueous solution, and stirring to react to obtain pretreated biomass; adding the pretreated starch and pretreated biomass, magnesium sulfate heptahydrate and zeolite into dilute hydrochloric acid, stirring the mixture at a high temperature for reaction by using an ethylene-octene copolymer and tetraethoxysilane, and sieving and drying the reaction product to obtain the sludge treating agent.
The anaerobic digestion performance of the sludge is obviously improved along with the prolonging of time and the accumulated gas production. The reason of gas generation is mainly that carbohydrate, soluble protein and the like are decomposed by bacteria to generate gas, wherein the pretreated starch grafted by the methacryloxytrimethyl ammonium chloride can influence the spiral structure of protein in the sludge, promote the formation of a loose protein molecular structure, improve the hydrophobicity of surface sludge and further improve the dehydration capability of the sludge. Also can enhance the decomposition of microorganisms. The biomass is added into dilute sulfuric acid, the acid group promotes cellulose expansion by forming a hydrophilic layer on the surface of the cellulose, the cellulose expansion can improve the internal surface area and expose more active substances in the biomass, so that the sodium bisulfite and the 2-naphthol-7-sodium sulfonate have higher reactivity to the biomass, the yield of total sugar in the biomass is improved, the utilization rate of the microorganism to carbohydrate is improved, and the gas yield is increased.
The mineralization of the sludge in the biological treatment process of the sludge treatment plant is insufficient, and the dehydration condition is poor. In this case, it is extremely difficult to reduce the water content to the lower level even by pressure filtration. In the invention, POE powder and methacryloxy trimethyl ammonium chloride are successfully grafted to a starch main chain, the ordered crystal structure of a starch skeleton is damaged, the surface of the starch shows a smooth elliptic three-dimensional structure, and gaps among particles are obvious. This may provide more active sites for sludge flocculation. The water in the sludge after the grafting of the methacryloxy trimethyl ammonium chloride is easy to remove. Mainly related to charge neutralization, adsorption bridging and hydrophobic groups during processing. The POE powder is introduced to provide active sites for positive charges and hydrophobic groups on the surface of the methacryloxy trimethyl ammonium chloride, and the improvement of the sludge dewatering efficiency is facilitated. The water in the sludge can be separated into free water and bound water, wherein the bound water includes capillary water, surface absorbed water and intracellular bound water. Free water is dispersed in sludge particles and is easily removed by gravity concentration, while bound water is hydrated in cells and is difficult to remove. The lower the compressibility of the sludge, the more porous structures are maintained, the deformation of the sludge is suppressed, and the release of the moisture of the sludge from the porous structures is promoted. Coconut shell, poplar sawdust and corn straw are stirred to react with sodium bisulfite and 2-naphthol-7-sodium sulfonate aqueous solution to condition the compression coefficient of sludge, so that a skeleton structure is formed in the sludge dewatering process, the strength of a flocculating constituent is improved, and a water drainage channel is constructed. After the biomass is treated by adding sodium bisulfite and 2-naphthol-7-sulfonic acid sodium salt aqueous solution, a large cavity structure is formed. This shortens the diffusion distance of water molecules, and has the effect of promoting the transfer of pyrolysis vapors. With further introduction of magnesium sulfate heptahydrate and zeolite, the presence of gallium (III) nitrate hydrate provides a suitable acid site and promotes aromatization reactions, acts to reduce mass transfer resistance and reduce surface acidity, and provides suitable active sites. The diffusion structure is retained and the diffusion effect of the water molecules is significantly enhanced. The invention reduces the production cost, and is a clean, environment-friendly and sustainable sludge treatment process.
Claims (8)
1. The sludge treatment process is characterized by comprising the following process steps in parts by weight:
step 1, adding 400-600 parts of sludge with the water content of 75-85% into a centralized treatment point, adding 3~8 parts of sludge treatment agent, and mixing to obtain a mixture;
step 2, adding the mixture prepared in the step 1 into a plate and frame filter press, pressing into a dry mixture, wherein the pressing pressure is 1.0-1.5 Mpa, the pressing time is 0.5-2h, then adding into a disc type dryer, the power of the disc type dryer is 150-200KW, the drying time is 2-5h, drying into a sludge mixture by using a natural gas boiler, the power of the natural gas boiler is 12-169w, the rated evaporation capacity is 3-5T/h, the drying temperature is 350-420 ℃, and generated odor is collected by washing and condensation;
step 3, adding the sludge mixture obtained in the step 2 into a mixer, adding 5-15 parts of sawdust biomass into the mixer, stirring and mixing, feeding into a rod forming machine to form sludge fuel rods, and feeding into a rod bin;
step 4, adding the sludge fuel rods prepared in the step 3 into an incinerator for pyrolysis and gasification treatment, cooling the generated flue gas by a waste heat boiler, treating the flue gas by a quench tower, a deacidification tower and a bag-type dust remover, and finally discharging the flue gas by a chimney to reach the standard and collecting slag;
the sludge treatment agent is prepared by the following method in parts by weight:
s1, adding 1.5 to 3 parts of industrial starch, 1~2 parts of POE powder and 0.2 to 0.5 part of methacryloxy trimethyl ammonium chloride into 20 to 40 parts of water, fully mixing, then introducing nitrogen for 3 to 8 hours at room temperature, wherein the nitrogen flow is 50 to 100L/h, then adding 0.005 to 0.02 part of ammonium persulfate, reacting at 60 to 70 ℃ for 4 to 8 hours, precipitating the reaction product by using 8 to 12 parts of acetone, filtering, separating, and drying in a vacuum oven at 50 to 70 ℃ for 1 to 3 hours to obtain pretreated starch;
s2, grinding 3~4 parts of the biomass turbid mixture into powder with the particle size of less than 0.4-0.8mm as a biomass raw material, drying at 100-120 ℃ for 10-30h, adding 10-20 parts of 1-4 wt% sulfuric acid aqueous solution into the biomass raw material, mixing, pretreating, adding 5-10 parts of 5-10 wt% sodium bisulfite aqueous solution, reacting for 10-30min, adding 2~5 parts of 3-7 wt% 2-naphthol-7-sulfonic acid sodium salt aqueous solution, and stirring and reacting for 1-3h to obtain pretreated biomass;
s3, adding the pretreated starch prepared in the step S1, the pretreated biomass prepared in the step S2, 0.1-0.5 part of magnesium sulfate heptahydrate and 0.1-0.2 part of zeolite into 20-40 parts of 1-3 mol/L hydrochloric acid, adding 0.4-0.6 part of ethylene-octene copolymer, stirring, dropwise adding 0.1-0.3 part of ethyl orthosilicate, stirring at 80-120 ℃ for 20-30h, centrifuging at 10000-14000rpm for 3-8min, collecting solid, drying at 80-120 ℃ overnight to obtain a crystalline material, soaking the crystalline material in 3~8 parts of 1-3 wt% gallium nitrate (III) aqueous solution, stirring at 20-30 ℃ for 10-20h, filtering and separating, and drying at 50-70 ℃ for 8-112h to obtain the sludge treatment agent.
2. The sludge treatment process according to claim 1, wherein the odor generated in the step 2 is supplied to the pyrolysis gasification incinerator in the step 4 by washing and condensing.
3. The sludge treatment process according to claim 1, wherein the pyrolysis gasification temperature in the step 4 is 700 to 900 ℃.
4. The sludge treatment process according to claim 1, wherein the bag-type dust collector in the step 4 is used for treating flue gas by adopting an activated carbon bag surface adsorption mode.
5. The sludge treatment process of claim 1 wherein the steam produced in step 4 is supplied to the tray dryer in step 2.
6. The sludge treatment agent is characterized by being prepared by the following method in parts by weight:
s1, adding 1.5 to 3 parts of industrial starch, 1~2 parts of POE powder and 0.2 to 0.5 part of methacryloxy trimethyl ammonium chloride into 20 to 40 parts of water, fully mixing, then introducing nitrogen for 3 to 8 hours at room temperature, wherein the nitrogen flow is 50 to 100L/h, then adding 0.005 to 0.02 part of ammonium persulfate, reacting at 60 to 70 ℃ for 4 to 8 hours, precipitating the reaction product by using 8 to 12 parts of acetone, filtering, separating, and drying in a vacuum oven at 50 to 70 ℃ for 1 to 3 hours to obtain pretreated starch;
s2, grinding 3~4 parts of the biomass turbid mixture into powder with the particle size of less than 0.4-0.8mm as a biomass raw material, drying at 100-120 ℃ for 10-30h, adding 10-20 parts of 1-4 wt% sulfuric acid aqueous solution into the biomass raw material, mixing, pretreating, adding 5-10 parts of 5-10 wt% sodium bisulfite aqueous solution, reacting for 10-30min, adding 2~5 parts of 3-7 wt% 2-naphthol-7-sulfonic acid sodium salt aqueous solution, and stirring and reacting for 1-3h to obtain pretreated biomass;
s3, adding the pretreated starch prepared in the step S1, the pretreated biomass prepared in the step S2, 0.1-0.5 part of magnesium sulfate heptahydrate and 0.1-0.2 part of zeolite into 20-40 parts of 1-3 mol/L hydrochloric acid, adding 0.4-0.6 part of ethylene-octene copolymer, stirring, dropwise adding 0.1-0.3 part of ethyl orthosilicate, stirring at 80-120 ℃ for 20-30h, centrifuging at 10000-14000rpm for 3-8min, collecting solid, drying at 80-120 ℃ overnight to obtain a crystalline material, soaking the crystalline material in 3~8 parts of 1-3 wt% gallium nitrate (III) aqueous solution, stirring at 20-30 ℃ for 10-20h, filtering and separating, and drying at 50-70 ℃ for 8-112h to obtain the sludge treatment agent.
7. The sludge treatment agent as claimed in claim 6, wherein the biomass raw material comprises coconut shells, poplar sawdust and corn stalks according to a mass ratio of 0.5 to 2:0.5 to 1: 1~2.
8. The sludge treatment agent according to claim 6, wherein the filtration separation is performed independently by filtration through a 300 to 500 mesh screen.
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