CN108569836B - Method and device for dehydrating and stabilizing chromium-containing sludge - Google Patents
Method and device for dehydrating and stabilizing chromium-containing sludge Download PDFInfo
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- CN108569836B CN108569836B CN201810435353.2A CN201810435353A CN108569836B CN 108569836 B CN108569836 B CN 108569836B CN 201810435353 A CN201810435353 A CN 201810435353A CN 108569836 B CN108569836 B CN 108569836B
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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
- C02F11/008—Sludge treatment by fixation or solidification
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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
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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
- 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
- C02F11/123—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering using belt or band filters
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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
- C02F11/127—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering by centrifugation
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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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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Abstract
The invention discloses a method and a device for stabilizing the dehydration of chromium-containing sludge. Specifically, pig manure is dried and pyrolyzed to obtain pig manure carbon; cooling the pig manure carbon, finely grinding the obtained pig manure carbon into pig manure carbon powder, and adding the pig manure carbon powder into chromium-containing sludge to be mixed to obtain a chromium-containing sludge mixture; condensing water vapor generated during drying of pig manure, and adding the condensed water into the obtained chromium-containing sludge mixture for slurry preparation to obtain mixed slurry; carrying out hydrothermal treatment on the mixed slurry to obtain a hydrothermal treatment product, and then carrying out solid-liquid separation; the liquid obtained by separation is used for anaerobic fermentation or directly enters a sewage treatment system to be treated and discharged after reaching the standard; and drying the solid obtained by separation to obtain the dehydrated stabilized chromium-containing sludge. The method and the equipment have simple flow and simple operation, the pig manure carbon is utilized to improve the dehydration performance of the chromium-containing sewage and solidify and stabilize the heavy metal chromium in the sludge, the treatment cost is low, and the final solid-phase product can be directly buried or used as a compost matrix or a raw material for preparing biochar or building materials, is green and environment-friendly, and has good social, economic and environmental benefits.
Description
Technical Field
The invention relates to a sludge treatment process, in particular to a method and a device for stabilizing the dehydration of chromium-containing sludge.
Background
The sludge with excessive chromium is a toxic and dangerous waste, is only treated by a common landfill method, and is easy to generate potential harm to the environment and human bodies. The heavy metal chromium can not only gather in the plant body and produce toxic action on the plant, but also influence the normal growth of the plant; under the action of biological chain, it can be enriched by times, and finally can be fed into human body, so that the protein in human body can be inactivated and denatured, and the human organ can be damaged. Therefore, the dehydration stabilization of the heavy metal chromium exceeding sludge has become a focus of attention. Currently, many techniques for sludge treatment include landfill, incineration, pyrolysis, building material utilization, and the like. However, in any treatment technology, two major problems of dehydration and heavy metal stabilization are solved firstly. The deep dehydration of the sludge is a process of reducing the water content of the sludge to below 60 percent by adopting certain mechanical equipment. Sludge is generally negatively charged and present in a colloidal form due to the presence of ionized functional groups such as carboxyl and phosphate groups, and is highly dispersed in water, making dewatering difficult. In order to realize deep dehydration of the sludge, the operation pressure of dehydration equipment cannot be increased, and how to improve the dehydration performance of the sludge needs to be considered. As shown in the prior researches, because the sludge has compressible characteristic, deep dehydration cannot be realized by simply maintaining high pressure, and chemical conditioning and dehydration property enhancement are very important for ensuring the efficiency of mechanical dehydration. In China, the deep dehydration of sludge and the development and research of additives have been reported. The invention patent Chinese patent application CN201610978602.3 discloses a sludge dewatering additive, a preparation process thereof and application thereof in sludge dewatering, wherein the additive consists of solid flue gas desulfurization gypsum and sodium sulfate accounting for 1-5% of the mass of the solid flue gas desulfurization gypsum, the addition amount is 10-20% of the solid content of biochemical sludge, the dehydration performance of the biochemical sludge is improved, and the sludge dewatering effect is improved. Chinese patent application CN201010580468.4 discloses a conditioner for dewatering domestic sludge, the formula of the conditioner comprises: polyacrylamide accounting for 0.3-0.9 percent of the dry weight of the sludge to be treated, bamboo charcoal accounting for 5-20 percent of the dry weight of the sludge to be treated, quaternary ammonium salt accounting for 0.2-1 percent of the dry weight of the sludge to be treated, quicklime accounting for 2-5 percent of the dry weight of the sludge to be treated and polyaluminium sulfate accounting for 5-20 percent of the dry weight of the sludge to be treated. CN107032580A discloses a sludge dewatering agent, which consists of a filter aid, a flocculating agent and peroxide, can remarkably reduce the specific resistance of sludge, and can reduce the water content to below 70% through mechanical filter pressing. Chinese patent application CN102145974A discloses a method for treating sludge in municipal sewage, which comprises the following steps: (1) adding an oxidation guiding agent and a regulator into sludge, stirring, introducing ozone, stirring for reaction, then adding a coagulation agent, and finally performing filter pressing on the sludge to obtain the sludge with the water content of less than 55%. In the technical scheme disclosed in the patent, most of the sludge dewatering auxiliary agents are inorganic chemical additives, so that the addition amount is large, the cost is high, and the application is limited. On the other hand, the control ways of the heavy metals in the sludge are mainly divided into removal and stabilization, wherein the stabilization process adopted for the sludge with the heavy metals with medium and low concentration has the characteristics of simple operation, low cost, wide application and the like. At present, some researches on the influence of additives on the form and stabilization of heavy metals in sludge are carried out, and partial additives have the tendency of converting the form of heavy metals in sludge into a residue state and reduce the harm to the environment. For example, Cao Zhong hong and other researches find that the addition of quick lime, fly ash and clay is beneficial to the conversion of Cr and Cd to stable forms in the sludge landfill process [ Cao Zhong hong and other researches. Chinese patent application CN201710610775.4 discloses a preparation and application method of a heavy metal sludge stabilizer, which comprises the following steps: (1) the preparation method comprises the following steps: by mass percentage, 10-50% of aggregate, 5-40% of precipitator and 1-10% of additive; (2) the application method comprises the following steps: adding water into the heavy metal sludge, stirring to form slurry, adjusting the pH of the slurry by using inorganic acid or inorganic base, adding 5-20% of the stabilizer obtained in the step (1), stirring uniformly, adding a curing agent, maintaining and detecting, wherein the leachate of the cured body reaches the standard of hazardous waste landfill. Chinese patent application CN201310449462.7 discloses a heavy metal sludge stabilizer and a use method thereof, the stabilizer is prepared by compounding 25-40% of inorganic alkaline substance, 20-30% of metal chelating agent and 40-45% of organic solvent, and the mixed soil added with the stabilizer is buried 2 meters underground. Chinese patent application CN201010145640.3 discloses a high compressive strength stabilized sludge, which is formed by adding a stabilizer and kaolin into dehydrated sludge and mixing, wherein the mass ratio of the dehydrated sludge, the stabilizer and the kaolin is 84-85: 11-12: 3-4, and the stabilizer is composed of cement and anhydrous sodium sulphate according to the mass ratio of 20: 1-2; the stabilized sludge can be subjected to landfill disposal and resource recycling according to actual needs, particularly has the characteristic of high compressive strength, can be used as a cover layer or a filling material of a landfill site, and can also be applied to other building aspects instead of building materials such as sand, clay and the like. The above patent is complex in process and high in cost for the solidification of heavy metals in sludge, and is not completely suitable for the harmless treatment of chromium-containing sludge. Therefore, the development of a low-cost and high-efficiency method and device for stabilizing the dehydration of the chromium-containing sludge is of great significance for realizing the harmless and resource utilization of the sludge polluted by heavy metals.
Disclosure of Invention
The invention aims to provide a method for stabilizing dehydration of chromium-containing sludge, which can effectively improve the dehydration performance of the chromium-containing sludge, realize stable solidification of heavy metal chromium, greatly reduce the risk of negative influence on the environment, has simple operation, obvious energy-saving benefit of the process and low treatment cost, lays a foundation for harmless treatment and subsequent resource utilization of heavy metal sludge, and has good economic benefit and environmental benefit. The method has the advantages of overcoming the defects of low dehydration efficiency, stable heavy metal solidification, high cost, easy generation of secondary pollution and the like of the conventional chromium-containing sludge treatment.
In order to achieve the aim, the invention provides a method for stabilizing the dehydration of chromium-containing sludge, which is characterized in that pig manure is dried, pyrolyzed and cooled to obtain pig manure carbon; finely grinding the obtained pig manure carbon into pig manure carbon powder, and adding the pig manure carbon powder into chromium-containing sludge to be mixed to obtain a chromium-containing sludge mixture; condensing water vapor generated during drying of pig manure, and adding the condensed water into the obtained chromium-containing sludge mixture for slurry preparation to obtain mixed slurry; carrying out hydrothermal treatment on the mixed slurry to obtain a hydrothermal treatment product, and then carrying out solid-liquid separation; the liquid obtained by separation is used for anaerobic fermentation or directly enters a sewage treatment system to be treated and discharged after reaching the standard; and drying the solid obtained by separation to obtain the dehydrated stabilized chromium-containing sludge.
Further, the pig manure is obtained by performing solid-liquid separation pretreatment on a farm; preferably, the water content of the pig manure is 40-50%;
optionally, the chromium-containing sludge is centrifugally dewatered chromium-containing sludge produced by an industrial sewage treatment plant, the water content is 80-90%, and the total chromium content is less than 10000 mg/kg.
Further, the drying temperature of the pig manure is 60-100 ℃, the drying time is 10-30min, and the water content after drying is less than 3%.
Further, the temperature of the pig manure pyrolysis treatment is 400-700 ℃, and the time of the pyrolysis treatment is 5-30 min.
In the cooling step, the cooling mode can be drum-type or tube bundle-type indirect cooling, and the final temperature of the pig manure carbon material obtained after cooling is less than 80 ℃;
optionally, the particle size of the pig manure powder is 100-200 meshes.
Further, the dry basis mass ratio of the pig manure carbon powder to the chromium-containing sludge is 5-10%;
optionally, the solid-liquid mass ratio of the mixed slurry is 8-15%.
Further, the temperature of the hydrothermal treatment is 160-220 ℃, the pressure is 1-5bar, and the time is 30-60 min;
optionally, the hydrothermal treatment product is subjected to solid-liquid separation by plate-and-frame filter pressing, vacuum filtration, centrifugal separation or belt filtration.
Furthermore, high-temperature flue gas generated by the heating furnace of the pyrolysis device is respectively used as an indirect heating heat source for the pig manure drying process, the hydrothermal treatment process and the solid phase drying process after the hydrothermal treatment.
Further, the solid phase drying temperature after the hydrothermal treatment is 80-120 ℃, and the time is 30-60 min.
The invention also provides a device for the method for stabilizing the chromium-containing sludge by dehydration, which is characterized by comprising a pig manure storage bin (1), a conveying device 1# (2), a drying device 1# (3), a conveying device 2# (4), a pyrolysis device (5), a cooling device (6), a conveying device 3# (7), a fine grinding device (8), a conveying device 4# (9), a condensing device (10), a liquid pump 1# (11) for 11, a chromium-containing sludge storage bin (12), a conveying device 5# (13), a mixing device (14), a conveying device 6# (15), a hydrothermal device (16), a separating device (17), a drying device 2# (18), a liquid pump 2# (19), a sewage treatment system (20), a conveying device 7# (21), a sludge storage bin (22) for stabilizing the chromium-containing sludge by dehydration and solidification, a combustion device (23), a fan 1# (24), and a fan, A fan 2# (25), a fan 3# (26) and a tail gas purification device (27);
wherein, the outlet of the pig manure storage bin (1) is connected with the inlet of a conveying device 1# (2); an outlet of the conveying device 1# (2) is connected with an inlet of the drying device 1# (3); a material outlet of the drying device 1# (3) is connected with an inlet of the conveying device 2# (4); the outlet of the conveying device 2# (4) is connected with the inlet of the pyrolysis device (5); the material outlet of the pyrolysis device (5) is connected with the inlet of the cooling device (6). The outlet of the cooling device (6) is connected with the inlet of the conveying device 3# (7); the outlet of the conveying device 3# (7) is connected with the inlet of the fine grinding device (8); the outlet of the fine grinding device (8) is connected with the inlet of the conveying device 4# (9); the outlet of the conveying device 4# (9) is connected with the inlet of the mixing device (14);
a steam outlet of the drying device 1# (3) is connected with an inlet of the condensing device (10); the liquid outlet of the condensing device (10) is connected with the inlet of a liquid pump 1# (11) 11, and the outlet of the liquid pump 1# (11) is connected with the inlet of a mixing device (14);
an outlet of the chromium-containing sludge storage bin (12) is connected with an inlet of a conveying device No. 5 (13); the outlet of the conveying device 5# (13) is connected with the inlet of the mixing device (14); the outlet of the mixing device (14) is connected with the inlet of the conveying device 6# (15); the outlet of the conveying device 6# (15) is connected with the inlet of the hydrothermal device (16); the outlet of the hydrothermal device (16) is connected with the inlet of the separation device (17); the solid phase outlet of the separation device (17) is connected with the inlet of a drying device 2# (18), the outlet of the drying device 2# (18) is connected with the inlet of a conveying device 7# (21), and the outlet of the conveying device 7# (21) is connected with a storage bin (22) for dehydrating, solidifying and stabilizing the chromium-containing sludge; the liquid phase outlet of the separation device (17) is connected with the inlet of a liquid pump 2# (19); the outlet of the liquid pump 2# (19) is connected with a sewage treatment system (20);
a pyrolysis gas outlet of the pyrolysis device (5) is connected with the combustion device (23), and heat generated by the combustion device (23) is used as energy of the pyrolysis device (5); the flue gas generated by the pyrolysis device (5) is respectively connected with the drying device 1# (3), the hydrothermal device (16) and the drying device 2# (18), and is pumped to the tail gas purification device (27) through the fan 1# (24), the fan 2# (25) and the fan 3# (26), so that the standard-reaching emission is realized;
further, the pig manure storage bin (1), the chromium-containing sludge storage bin (12) and the dehydration, solidification and stabilization chromium-containing sludge storage bin (22) are common steel square bins or round bins;
optionally, the conveying device 1# (2), the conveying device 2# (4), the conveying device 3# (7), the conveying device 4# (9) and the conveying device 7# (21) are single-shaft screw conveying devices, double-shaft screw conveying devices or shaftless screw conveying devices;
optionally, the conveying device 5# (13) and the conveying device 6# (15) are slurry pumps;
optionally, the drying device 1# (3) and the drying device 2# (18) can be a disc dryer, a drum dryer or other forms of flue gas indirect heating drying devices;
optionally, the pyrolysis device (5) is a roller heating device, and the heating mode is indirect heating;
optionally, the cooling device (6) is a roller cooler, a tube bundle type cooling heat exchange device or other forms of air or water indirect cooling devices;
optionally, the fine grinding device (8) is a Raymond mill, a horizontal roll mill, a ball mill and an air flow mill;
optionally, the condensing unit (10) is an indirect condensing unit;
optionally, the liquid pump 1# (11) and the liquid pump 2# (19) are common water pumps;
optionally, the mixing device (14) is a common stainless steel mixing tank with a mechanical stirring device;
optionally, the hydrothermal device (16) is a common indirect heating type hydrothermal reaction kettle;
optionally, the separation device (17) is a plate-and-frame filter press, a vacuum suction filter, a centrifugal separator or a belt filter press;
optionally, the sewage treatment system (20) is an existing conventional sewage treatment process system;
optionally, the combustion device (23) is a gas combustion furnace;
optionally, the fan 1# (24), the fan 2# (25) and the fan 3# (26) are all common fans;
optionally, the tail gas purification device (27) is a common double alkali tail gas purification system.
The method adopts the pig manure to prepare the carbon, so that on one hand, the harmless treatment of the pig manure can be realized, and on the other hand, the mixed water of the pig manure carbon and the sludge has good effects of improving the sludge dewatering performance and realizing the solidification stability of heavy metal chromium after the name is improved.
The drying temperature of the pig manure is 60-100 ℃, the drying time is 10-30min, and the water content after drying is less than 3%. After drying until the water content is less than 3%, carrying out pyrolysis carbonization so as to save energy; in addition, the pig manure with high water content is directly pyrolyzed and carbonized under the high-temperature condition, so that gasification reaction is easy to generate, and the yield of pig manure charcoal is reduced.
The particle size of the pig manure carbon powder is 100-200 meshes. In the hydrothermal process, the effect with the chromium-containing sludge is more sufficient, and the aim of solidifying and stabilizing the chromium-containing sludge is fulfilled; experiments show that the particle size is more than 100 meshes, and the effect is not obvious; the grain diameter is less than 200 meshes, the fine grinding energy consumption is large, and the effect of stabilizing the dehydration of the chromium-containing sludge is not obviously improved.
The dry basis mass ratio of the pig manure carbon powder to the chromium-containing sludge is 5-10%; when the adding proportion of the pig manure carbon powder is less than 5 percent, the chromium solidification stabilizing effect is not obvious; when the adding proportion of the pig manure carbon powder is more than 10%, the adding amount of the pig manure carbon is large, the cost is high, and the method is uneconomical.
The solid-liquid mass ratio of the mixed slurry is 8-15%. Under the condition of the solid-liquid mass ratio, the hydrothermal reaction effect is good; when the solid-liquid mass ratio of the mixed slurry is less than 8%, the water content is too high, the water treatment efficiency is reduced, and the cost is higher; the solid-liquid mass ratio of the mixed slurry is more than 15%, the solid content is too high, and the dehydration performance of the sludge containing chromium and the solidification stabilizing effect of chromium after hydrothermal reaction are not sufficient.
In order to realize the drying treatment and further reduction of the chromium-containing sludge after the hydrothermal treatment, the solid phase drying temperature after the hydrothermal treatment is 80-120 ℃ and the time is 30-60 min.
The invention has the beneficial effects that: the pig manure and the chromium-containing sludge are used as main raw materials, the pig manure is pyrolyzed to obtain pig manure carbon, and then the pig manure carbon and the chromium-containing sludge are mixed for hydrothermal treatment, so that the special porous structure and rich functional groups of the pig manure carbon are fully utilized, on one hand, the absorption, precipitation, complexation and the like of heavy metal chromium are realized, the heavy metal chromium residue state content in the sludge is obviously improved, the heavy metal chromium is fully solidified and stabilized, the environmental risk is greatly reduced, and the harmless treatment of the chromium-containing sludge is realized; on the other hand, the pig manure carbon reduces the electrostatic repulsion and hydration among sludge particles, forms a permeable and firm lattice structure in the mixed hydrothermal process, realizes the rapid cell wall breaking of the sludge hydrothermal process, rapidly releases capillary water, adsorbed water and internal water, greatly reduces the solid phase viscosity of the sludge, greatly improves the dehydration property, and ensures the permeability of a filter phase in the subsequent dehydration process, thereby improving the dehydration efficiency in the solid-liquid separation stage, and the improvement range is over 50%; moreover, the drying efficiency of the dewatered sludge is obviously improved. In addition, pyrolysis gas generated by pyrolysis of the pig manure is used as fuel in the pyrolysis process of the pig manure, and external energy sources are not needed; the waste heat of hot flue gas generated in the pyrolysis process is utilized in the drying process and the hydrothermal process, and the energy-saving benefit of the process is remarkable. The whole process equipment flow is simple and direct, the circular economy and clean production concept is fully reflected, the operation is simple, the operation cost is low, the final product can be directly buried, and can also be used as a compost substrate or a raw material for preparing biochar or building materials, the aims of recycling and harmlessness of the chromium-containing sludge are fulfilled, the environment is protected, and good social benefit, economic benefit and environmental benefit are achieved.
Drawings
FIG. 1 is a process flow chart of a method for stabilizing and dewatering chromium-containing sludge according to an embodiment of the present invention.
FIG. 2 is a diagram showing the equipment connection of an apparatus for carrying out a method for stabilizing and dewatering chromium-containing sludge according to an embodiment of the present invention.
FIG. 3 is a graph showing the results of a viscosity test of sludge under different treatment conditions in example 2 of the present invention.
FIG. 4 is a BCR morphology distribution diagram of heavy metal chromium in sludge under different sludge treatment conditions in example 2 of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
FIG. 1 is a process flow chart of a method for stabilizing and dewatering chromium-containing sludge according to an embodiment of the present invention: drying and pyrolyzing pig manure obtained by solid-liquid separation pretreatment of a farm to obtain pig manure carbon; finely grinding the pig manure carbon, and adding the pig manure carbon into the chromium-containing sludge in proportion for mixing; condensing water vapor generated by drying pig manure, and adding the condensed water into a mixture of pig manure carbon and chromium-containing sludge for slurry preparation; carrying out hydro-thermal treatment on the mixed slurry obtained by slurry preparation, and then carrying out solid-liquid separation; the liquid obtained by separation can be used for anaerobic fermentation, and can also be directly discharged after entering a sewage treatment system for treatment and reaching the standard; the solid obtained by separation is the dehydrated stabilized chromium-containing sludge, the dehydration performance is obviously enhanced, the residue state of heavy metal chromium is obviously increased, the dehydration stabilization is completely realized, and the solid can be directly buried and also can be used as a compost matrix or a raw material for preparing biochar or building materials.
FIG. 2 is a diagram showing the equipment connection of an apparatus for carrying out a method for stabilizing and dewatering chromium-containing sludge according to an embodiment of the present invention. Wherein, 1 is a pig manure storage bin; 2 is conveying device 1 #; 3 is drying apparatus 1 #; 4 is conveying means 2 #; 5 is a pyrolysis unit; 6 is a cooling device; 7 is conveying means 3 #; 8 is a fine grinding device; 9 is conveying means 4 #; 10 is a condensing unit; 11 is liquid pump 1 #; 12 is a chromium-containing sludge storage bin; 13 is conveying means 5 #; 14 is a mixing device; 15 is conveying device 6 #; 16 is a hydrothermal apparatus; 17 is a separation device; 18 is drying apparatus 2 #; 19 is liquid pump 2 #; 20 is a sewage treatment system; 21 is the conveying device 7 #; 22 is a storage bin for dehydrating, solidifying and stabilizing the chromium-containing sludge; 23 is a combustion device; 24 is fan 1 #; 25 is fan 2 #; 26 blower 3 #; and 27 is an exhaust gas purifying device.
The invention relates to a device for dehydrating and stabilizing chromium-containing sludge, which comprises a pig manure storage bin (1), a conveying device 1# (2), a drying device 1# (3), a conveying device 2# (4), a pyrolysis device (5), a cooling device (6), a conveying device 3# (7), a fine grinding device (8), a conveying device 4# (9), a condensing device (10), a liquid pump 1# (11) 11, a chromium-containing sludge storage bin (12), a conveying device 5# (13), a mixing device (14), a conveying device 6# (15), a hydrothermal device (16), a separating device (17), a drying device 2# (18), a liquid pump 2# (19), a sewage treatment system (20), a conveying device 7# (21), a dehydration solidification stabilization chromium-containing sludge storage bin (22), a combustion device (23), a fan 1# (24), a fan 2# (25), a fan 3# (26), An exhaust gas purification device (27).
Wherein, the outlet of the pig manure storage bin (1) is connected with the inlet of a conveying device 1# (2); an outlet of the conveying device 1# (2) is connected with an inlet of the drying device 1# (3); a material outlet of the drying device 1# (3) is connected with an inlet of the conveying device 2# (4); the outlet of the conveying device 2# (4) is connected with the inlet of the pyrolysis device (5); the material outlet of the pyrolysis device (5) is connected with the inlet of the cooling device (6). The outlet of the cooling device (6) is connected with the inlet of the conveying device 3# (7); the outlet of the conveying device 3# (7) is connected with the inlet of the fine grinding device (8); the outlet of the fine grinding device (8) is connected with the inlet of the conveying device 4# (9); the outlet of the conveying device 4# (9) is connected with the inlet of the mixing device (14).
A steam outlet of the drying device 1# (3) is connected with an inlet of the condensing device (10); the liquid outlet of the condensing device (10) is connected with the inlet of a liquid pump 1# (11) 11, and the outlet of the liquid pump 1# (11) is connected with the inlet of a mixing device (14).
An outlet of the chromium-containing sludge storage bin (12) is connected with an inlet of a conveying device No. 5 (13); the outlet of the conveying device 5# (13) is connected with the inlet of the mixing device (14); the outlet of the mixing device (14) is connected with the inlet of the conveying device 6# (15); the outlet of the conveying device 6# (15) is connected with the inlet of the hydrothermal device (16); the outlet of the hydrothermal device (16) is connected with the inlet of the separation device (17); the solid phase outlet of the separation device (17) is connected with the inlet of a drying device 2# (18), the outlet of the drying device 2# (18) is connected with the inlet of a conveying device 7# (21), and the outlet of the conveying device 7# (21) is connected with a storage bin (22) for dehydrating, solidifying and stabilizing the chromium-containing sludge; the liquid phase outlet of the separation device (17) is connected with the inlet of a liquid pump 2# (19); the outlet of the liquid pump 2# (19) is connected with a sewage treatment system (20);
a pyrolysis gas outlet of the pyrolysis device (5) is connected with the combustion device (23), and heat generated by the combustion device (23) is used as energy of the pyrolysis device (5); the flue gas generated by the combustion device (23) is respectively connected with the drying device 1# (3), the hydrothermal device (16) and the drying device 2# (18), and is pumped to the tail gas purification device (27) through the fan 1# (24), the fan 2# (25) and the fan 3# (26), so that the standard emission is realized.
The device comprises a pig manure storage bin (1), a conveying device 1# (2), a drying device 1# (3), a conveying device 2# (4), a pyrolysis device (5), a cooling device (6), a conveying device 3# (7), a fine grinding device (8), a conveying device 4# (9), a condensing device (10), a liquid pump 1# (11) 11, a chromium-containing sludge storage bin (12), a conveying device 5# (13), a mixing device (14), a conveying device 6# (15), a hydrothermal device (16), a separating device (17), a drying device 2# (18), a liquid pump 2# (19), a sewage treatment system (20), a conveying device 7# (21), a dehydration solidification stable chromium-containing sludge storage bin (22), a combustion device (23), a fan 1# (24), a fan 2# (25), a fan 3# (26) and a tail gas purification device (27).
The pig manure storage bin (1), the chromium-containing sludge storage bin (12) and the dehydration, solidification and stabilization chromium-containing sludge storage bin (22) are common steel square bins or round bins. The conveying device 1# (2), the conveying device 2# (4), the conveying device 3# (7), the conveying device 4# (9), and the conveying device 7# (21) are single-shaft screw conveying devices, double-shaft screw conveying devices, or shaftless screw conveying devices. The conveying devices 5# (13) and 6# (15) are slurry pumps. The drying device 1# (3) and the drying device 2# (18) can be a disc dryer, a drum dryer or other forms of flue gas indirect heating drying devices. The pyrolysis device (5) is a roller heating device, and the heating mode is indirect heating. The cooling device (6) is a roller cooler, a tube bundle type cooling heat exchange device or other air or water indirect cooling devices. The fine grinding device (8) is a Raymond mill, a horizontal roller mill, a ball mill and an air flow mill; the condensing device (10) is an indirect condensing device. The liquid pump 1# (11) and the liquid pump 2# (19) are common water pumps. The mixing device (14) is a common stainless steel mixing tank with a stirring device. The hydrothermal device (16) is a common indirect heating type hydrothermal reaction kettle; the separation device (17) is a vacuum suction filter, a belt filter press, a centrifugal separator or a plate-and-frame filter press; the sewage treatment system (20) is an existing traditional sewage treatment process system. The combustion device (23) may be a gas combustion heating furnace. The blower 1# (24), the blower 2# (25) and the blower 3# (26) are all common blowers. The tail gas purification device (27) is a common double-alkali tail gas purification system.
The following examples were carried out in conjunction with FIGS. 1-2 and the apparatus for dewatering and stabilizing chromium-containing sludge.
Example 1:
drying and pyrolyzing pig manure obtained by solid-liquid separation pretreatment of a farm to obtain pig manure carbon; finely grinding the pig manure carbon, and adding the pig manure carbon into the chromium-containing sludge in proportion for mixing; condensing water vapor generated by drying pig manure, and adding the condensed water into a mixture of pig manure carbon and chromium-containing sludge for slurry preparation; carrying out hydro-thermal treatment on the mixed slurry obtained by slurry preparation, and then carrying out solid-liquid separation; the liquid obtained by separation can be used for anaerobic fermentation, and can also be directly discharged after entering a sewage treatment system for treatment and reaching the standard; the dehydration performance of the solid obtained by separation is obviously improved, the residue state of the heavy metal chromium is obviously increased, the heavy metal chromium is stably solidified, and the final product after drying is the dehydrated stable Cr-containing sludge which can be directly buried and can also be used as a compost matrix or a raw material for preparing biochar or building materials. The pig manure is obtained by solid-liquid separation pretreatment in a farm, and the water content is 40-50%; the chromium-containing sludge is centrifugally dewatered chromium-containing sludge produced by industrial sewage treatment plants, the water content is 80-90%, and the total chromium content is less than 10000 mg/kg. The drying temperature of the pig manure is 60-100 ℃, the drying time is 10-30min, and the water content after drying is less than 3%; the water vapor evaporated by drying is condensed and recovered and can be used for mixing water for the size mixing process. The pyrolysis temperature is 400-700 ℃, and the material retention time is 5-30 min; in the cooling recovery step, the cooling mode can be drum-type or tube bundle-type indirect cooling, and the final temperature of the pig manure carbon material obtained after cooling is less than 80 ℃; the particle size of the powder obtained after the pig manure carbon is finely ground is controlled to be 100-200 meshes. In the mixing and size mixing process, the mass ratio of the pig manure carbon powder to the chromium-containing sludge is 5-10%, and the solid-liquid ratio after mixing and size mixing is 8-15%. The hydrothermal treatment process comprises the steps of performing hydrothermal treatment at the temperature of 160-220 ℃, at the pressure of 1-5bar and for 30-60 min; the solid-liquid separation method of the hydrothermal treatment product is plate-frame filter pressing, vacuum filtration, centrifugal separation or belt filtration. The high-temperature flue gas generated by the heating furnace of the pyrolysis device is respectively used as an indirect heating heat source for the pig manure drying process, the hydrothermal treatment process and the solid phase drying process after the hydrothermal treatment, and the energy cascade utilization is fully realized. After the hydrothermal treatment, the solid phase is dried at the temperature of 80-120 ℃ for 30-60 min.
The chromium-containing sludge after dehydration and stabilization is subjected to heavy metal leaching toxicity determination by adopting a TCLP (toxin chromatography) toxicity leaching method established by the United states Environmental Protection Agency (EPA), and the environmental safety of the new process is evaluated, and the results are shown in Table 1.
TABLE 1 table of heavy metal chromium leaching concentration before and after sludge treatment by TCLP method
As can be seen from Table 1, the leaching content of TCLP of heavy metal Cr in the Cr-containing sludge before treatment far exceeds the limit value specified by the standard, but the leaching amount of the heavy metal Cr is greatly reduced after dehydration stabilization treatment by the method disclosed by the invention and is lower than the US-EPA standard, no environmental risk exists, and harmless treatment is realized; on the other hand, the TCLP leaching content of heavy metal Cr in the dewatered and stabilized Cr-containing sludge is also lower than the limit value of the hazardous waste identification standard GB5085.3-2007, and the treated final product can be directly buried as a general waste, and can also be used as a compost matrix or a raw material for preparing biochar or building materials.
Example 2
Drying and pyrolyzing pig manure obtained by solid-liquid separation pretreatment of a farm to obtain pig manure carbon; mixing pig with pig meatFinely grinding the fecal carbon, and adding the fecal carbon into the chromium-containing sludge in proportion for mixing; condensing water vapor generated by drying pig manure, and adding the condensed water into a mixture of pig manure carbon and chromium-containing sludge for slurry preparation; carrying out hydro-thermal treatment on the mixed slurry obtained by slurry preparation, and then carrying out solid-liquid separation; the liquid obtained by separation can be used for anaerobic fermentation, and can also be directly discharged after entering a sewage treatment system for treatment and reaching the standard; the solid obtained by separation has enhanced dehydration property, obviously increases the residue state of heavy metal chromium, and completely realizes the dehydration stabilization of the chromium-containing sludge. The final product after drying, namely the dehydrated and stabilized Cr-containing sludge, can be directly buried, and also can be used as a compost matrix or a raw material for preparing biochar or building materials. The pig manure is obtained by solid-liquid separation pretreatment of a farm, and the water content is 45%; the chromium-containing sludge is centrifugally dewatered chromium-containing sludge produced by industrial sewage treatment plants, has the water content of 85 percent and the chromium content of 6350 mg-kg-1. The drying temperature of the pig manure is 100 ℃, the drying time is 30min, and the water content is obtained after drying<3 percent; the water vapor evaporated by drying is condensed and recovered and is used for mixing water used in the size mixing process. The pyrolysis temperature is 600 ℃, and the material retention time is 25 min; in the cooling and recycling step, the cooling mode can be drum-type or tube bundle-type indirect cooling, and the final temperature of the pig manure carbon material is obtained after cooling<80 ℃; the particle size of the powder obtained after the pig manure carbon is finely ground is controlled to be 100-200 meshes. In the mixing and size mixing process, the mass ratio of the pig manure carbon powder to the chromium-containing sludge is 10%, and the solid-liquid ratio after mixing and size mixing is 8%. In the hydrothermal treatment process, the temperature of the hydrothermal treatment is respectively 160 ℃, 180 ℃,200 ℃, 220 ℃, the pressure is 4.0bar, the time is 30min, and the treatment process is named as sludge carbonization according to different treatment schemes160Adding carbon into sludge180Adding carbon into sludge200Adding carbon into the sludge220For comparison with raw sludge; the solid-liquid separation method of the hydrothermal treatment product is centrifugal separation, and the separated solid phase is subjected to a sludge viscosity test to represent the sludge dewatering performance.
The results of the viscosity test of the sludge under different treatment conditions are shown in fig. 3. The results show that compared with the original sludge, the sludge viscosity shows a trend of obviously and greatly decreasing along with the increase of the temperature after the mixed hydrothermal treatment with the pig manure carbon powder; because the viscosity of the sludge is in a negative correlation with the dehydration performance, the chromium-containing sludge and the pig manure carbon are mixed for hydrothermal treatment, so that the dehydration performance of the sludge is greatly improved.
The morphological distribution of heavy metal elements in sludge is divided into four components, weak acid state (exchangeable state and carbonate-bound state), reducible state (iron-manganese oxide-bound state), oxidizable state (organic matter and sulfide-bound state) and residue state, by a BCR continuous extraction method supported by The European Commission on Standard test and analysis (The New The Standards, measures and Testing programs). Heavy metals in weak acid extraction state and reducible state are easily absorbed by plants, and bring negative influence on ecological environment; the oxidizable state is a state that metal ions are combined with organic matters and sulfides, organic matter active groups are used as ligands to be combined or insoluble substances generated by sulfur ions and metal particles are used, and when the organic matters react under the oxidation condition, part of metals are released. The solid in the residue contains the solid which can mainly solidify the metal in a crystal structure, so the heavy metal in the residue state is considered to be the most stable metal state; when the content of the metal residue in the sample is increased, the metal residue is shown to exist more stably in the environment and is not easy to cause environmental risks. The BCR test results are shown in fig. 4.
The results of FIG. 4 show that, compared with the original sludge, the chromium-containing sludge is subjected to hydrothermal mixing with pig manure carbon, so that heavy metal chromium in the sludge is converted from an unstable state to a residual state, the content of the residual state is obviously improved, the unstable state is obviously reduced, and the solidification and stabilization of the heavy metal chromium are realized.
The device for dehydrating and stabilizing the chromium-containing sludge can improve the dehydration performance of the chromium-containing sludge, realizes stable solidification of heavy metal chromium, greatly reduces the risk of negative influence on the environment, is simple to operate, has obvious energy-saving benefit in the process and low operation cost, can be used for harmless treatment of the heavy metal chromium-exceeding sludge, can control the TCLP leaching content of the heavy metal chromium within the limit value of the hazardous waste identification standard GB5085.3-2007, can treat the final product as a general waste, lays a foundation for subsequent further resource utilization, and has good economic benefit and environmental benefit.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Claims (7)
1. A dehydration stabilization method of chromium-containing sludge is characterized in that pig manure is dried until the moisture content is less than 3%, then is pyrolyzed at 400-700 ℃ for 5-30min and is cooled to obtain pig manure carbon; finely grinding the obtained pig manure carbon into pig manure carbon powder, and adding the pig manure carbon powder into chromium-containing sludge to be mixed to obtain a chromium-containing sludge mixture; the dry basis mass ratio of the pig manure carbon powder to the chromium-containing sludge is 5-10%; condensing water vapor generated during drying of pig manure, and adding the condensed water into the obtained chromium-containing sludge mixture for slurry preparation to obtain mixed slurry; the solid-liquid mass ratio of the mixed slurry is 8-15%; carrying out hydrothermal treatment on the mixed slurry to obtain a hydrothermal treatment product, and then carrying out solid-liquid separation, wherein the temperature of the hydrothermal treatment is 160-220 ℃, the pressure is 1-5bar, and the time is 30-60min, and the solid-liquid separation method comprises plate-and-frame filter pressing, vacuum filtration, centrifugal separation or belt filtration; the liquid obtained by separation is used for anaerobic fermentation or directly enters a sewage treatment system to be treated and discharged after reaching the standard; drying the solid obtained by separation to obtain dehydrated stabilized chromium-containing sludge;
the chromium-containing sludge is centrifugally dewatered chromium-containing sludge produced by an industrial sewage treatment plant, the water content is 80-90%, and the total chromium content is less than 10000 mg/kg.
2. The method for stabilizing and dewatering chromium-containing sludge according to claim 1, wherein the pig manure is pig manure obtained by solid-liquid separation pretreatment in a farm.
3. The method for stabilizing and dewatering chromium-containing sludge according to claim 2, wherein the water content of the pretreated pig manure is 40-50%.
4. The method for stabilizing and dehydrating chromium-containing sludge according to claim 1, wherein the drying temperature of the pig manure is 60-100 ℃ and the drying time is 10-30 min.
5. The method for stabilizing the dehydration of the chromium-containing sludge according to claim 1, wherein in the cooling step, the cooling mode is drum-type or tube bundle-type indirect cooling, and the final temperature of the pig manure carbon material obtained after cooling is less than 80 ℃; the particle size of the pig manure carbon powder is 100-200 meshes.
6. The method of claim 1, wherein the high temperature flue gas generated by the pyrolysis device heating furnace is used as an indirect heating source for the pig manure drying step, the hydrothermal treatment step and the post-hydrothermal solid drying step.
7. The method for stabilizing and dewatering chromium-containing sludge according to claim 1, wherein the drying temperature of the solids after the hydrothermal treatment is 80-120 ℃ and the drying time is 30-60 min.
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| CN109970064A (en) * | 2019-02-19 | 2019-07-05 | 同济大学 | A kind of urban mud anaerobic digestion biogas residue reduction prepares the device of silicon carbide |
| CN110092559A (en) * | 2019-04-10 | 2019-08-06 | 浙江清风源环保科技有限公司 | A kind of processing method of sludge containing heavy metal |
| CN111735062B (en) * | 2020-06-29 | 2021-11-16 | 中国科学院过程工程研究所 | Low-pollution-emission sludge resource incineration method and system device |
| CN112830656A (en) * | 2021-02-04 | 2021-05-25 | 中国科学院城市环境研究所 | Method and device for cooperatively treating sludge and livestock and poultry manure |
| CN114249514B (en) * | 2021-12-06 | 2024-01-23 | 中国科学院城市环境研究所 | Harmless recycling method and device for tanning chromium-containing sludge |
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