CN109928593B - Method for deep dehydration of sludge hot water decoupling combined framework material - Google Patents
Method for deep dehydration of sludge hot water decoupling combined framework material Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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Abstract
The invention discloses a method for deep dehydration of sludge by coupling a pyrohydrolysis technology with a framework material technology, which comprises the steps of carrying out hydrothermal liquefaction on Fenton iron mud in an ammonia water system to obtain aminated Fenton carbon as a framework material, wherein the hydrothermal liquefaction reaction temperature of the Fenton iron mud is 280-340 ℃, the reaction time is 30-90 min, the mass ratio of the Fenton iron mud to 28% ammonia water is 1: 0.5-1.5, carrying out vacuum filtration, drying and grinding to obtain the aminated Fenton carbon. Mixing and uniformly stirring sludge with the water content of 80-85% and an aminated Fenton carbon framework material, wherein the mass ratio of dry-based sludge to the framework material is 0.3-1.2; adding the mixture into a hydrothermal reaction kettle for reaction at 160-200 ℃ for 30-90 min, wherein the mass ratio of the sludge mixture to water is 1: 0.5-1.5, and performing vacuum filtration dehydration after the reaction, wherein the dehydration rate of the sludge treated by the method is more than 50%. The method disclosed by the invention is simple in process and convenient to operate, is beneficial to improving sludge dewatering and Fenton iron mud resource application, and is beneficial to industrial production.
Description
Technical Field
The invention relates to the technical field of environmental engineering and sludge treatment, in particular to a method for deep dehydration of sludge by a hydrothermal method.
Background
At present, with the increasing of the national environment protection work, the sewage treatment rate in China is obviously improved, however, along with the sewage treatment, the problem of sludge treatment is brought, about 4000 ten thousand tons of wet sludge (80% of water content) is generated in China every year, the data is continuously increased, and the annual output of municipal sludge in China is estimated to reach 6000 to 9000 ten thousand tons in 2020, and the treatment rate is less than 60%. The sludge carries a large amount of organic pollutants, parasitic ova, pathogenic microorganisms, heavy metals and other substances, percolate is extremely easy to generate in the processes of storage, transportation, treatment and the like to pollute water sources, the generated volatile gas pollutes the atmosphere, and the pollution of the volatile gas to the environment is not inferior to that of sewage.
The water content of the sludge after mechanical filter pressing is still high and is usually 80-85%, so that the sludge dewatering and reducing treatment becomes the first and extremely important step in the sludge treatment process. The conventional methods include a heat drying method, an anaerobic digestion method, a thermal hydrolysis method and the like. The mechanical dehydration method is a main dehydration scheme of the sludge at present, mainly utilizes the gravity, the centrifugal force, the pressure, the suction force and the like of machinery to separate water in the sludge, but the mechanical dehydration is limited, and organic matters, pathogenic microorganisms and the like in the sludge cannot be destroyed or removed by the mechanical dehydration method (CN 108249720A, CN 104556621A); the heat drying method removes water in sludge by heating, although the dehydration rate is high, the energy consumption is large, and malodorous gases such as NH3 and H2S are easily generated in the heating dehydration process to cause secondary pollution (CN 105668980A and CN 107827334A); anaerobic digestion and thermal hydrolysis are novel and green sludge dewatering and treatment technologies, the anaerobic digestion decomposes organic matters in sludge into methane and carbon dioxide under the combined action of facultative bacteria and anaerobic bacteria under the anaerobic condition, the organic matter content in the sludge is reduced, the sludge dewatering rate is improved, useful byproducts such as methane can be generated, and the method has a good application prospect, but the sludge treatment efficiency is relatively low (CN 108358429A, CN 108164124A); the thermal hydrolysis treatment is mainly to promote the hydrolysis of organic matters such as protein in the sludge to destroy extracellular polymers and release intracellular water in the sludge by using the change of the dielectric constant of water under the conditions of high temperature and high pressure, so as to achieve the aim of effectively dehydrating the sludge, but the thermal hydrolysis dehydration rate of most of the sludge is lower than 50 percent at present (CN1569699A, CN 108623119A). Mainly because sludge dewatering is limited to a certain extent by the incomplete destruction of the extracellular polymeric structure of the sludge. The sludge is easy to deform in the compression process due to certain viscoelasticity, and the aim of effective filter pressing dehydration cannot be fulfilled. Framework materials or filter aids are commonly used for improving the viscoelasticity of sludge, improving the compressibility of the sludge, improving the mechanical strength and permeability of sludge solids in the compression process and achieving the purpose of deep dehydration, and commonly used are inorganic materials, agricultural and forestry wastes and the like (CN 108929023A, CN107032580A, CN 106045271A). Although the addition of the framework material is helpful for sludge dehydration, the mechanical filter pressing time is long, the energy consumption is relatively high, and the heat value of the sludge filter cake as a solid fuel is obviously reduced after the inorganic framework material is added. Although partial dehydration of the sludge can be realized by the current Fenton oxidation or Fenton-like oxidation process treatment, deep dehydration cannot be realized, and the water content of the sludge is still over 70 percent generally.
At present, although various schemes are used for deep dehydration of sludge, few and few sludge dehydration schemes which can really and effectively carry out industrial treatment are available. Therefore, the practical sludge deep dehydration scheme with application significance is found to be of great significance.
Disclosure of Invention
The purpose of the invention is as follows: in order to solve the technical scheme, the invention discloses a method for deep dehydration of sludge by coupling a sludge pyrohydrolysis technology with a framework material technology.
The technical scheme is as follows: the invention discloses a scheme for deep dehydration of sludge by coupling a pyrohydrolysis technology with a framework material, which is characterized by comprising the following steps of: deep dehydration is carried out on the sludge by a pyrohydrolysis technology and coupling of a framework material, and the method comprises the following steps:
(1) mixing sludge to be treated with the water content of 80-85% and aminated Fenton carbon serving as a framework material, and uniformly stirring to obtain a sludge mixture, wherein the mass ratio of dry-based sludge to the framework material is 1: (0.3 to 1.2);
(2) adding the sludge mixture obtained in the step (1) into a hydrothermal reaction kettle, and ensuring that the effective volume is below 80%, the hydrothermal liquefaction reaction temperature is 160-200 ℃, and the reaction time is 30-90 min;
(3) and (3) dehydrating the reaction product obtained in the step (2) to obtain filtrate and a dehydrated sludge filter cake.
Further, the framework material is aminated Fenton carbon obtained by the hydro-thermal liquefaction of Fenton iron mud.
Further, the Fenton iron mud is ferric iron-containing mud obtained after a Fenton oxidation process in the sewage treatment process.
Further, the preparation steps of preparing the aminated Fenton carbon by the Fenton iron mud through hydrothermal liquefaction are as follows:
(1.1) mixing and uniformly stirring fenton iron mud and ammonia water, wherein the mass ratio of the fenton iron mud to the ammonia water is 1: 0.5-1.5;
(1.2) adding the mixture obtained in the step (1) into a hydrothermal reaction kettle, ensuring that the effective volume is below 80%, and then carrying out hydrothermal liquefaction reaction at the reaction temperature of 280-340 ℃ for 30-90 min;
(1.3) dehydrating the reaction product obtained in the step (2) to obtain filtrate and a solid product, washing the solid product with distilled water, drying at 100 ℃ for 24 hours, and grinding into powder.
Further, the ammonia water mass concentration in the step (1.1) is 28%.
Further, the mass ratio of the sludge mixture to the water in the step (2) is 1: 0.5-1.5.
Further, the granularity of the aminated Fenton carbon after grinding and sieving is 100-300 meshes of screen underflow.
The invention utilizes the thermal hydrolysis technology, and the framework material containing amino (-NH2) is used as the catalyst, thereby promoting the hydrolysis of extracellular polymers in the sludge and realizing the deep dehydration under the condition of the existence of the framework material; meanwhile, the aminated Fenton carbon skeleton material disclosed by the invention not only can enhance the compressibility of sludge in the sludge dehydration process, but also contains amino (-NH2), so that the hydrolysis of extracellular polymers in the sludge is promoted, and the dehydration rate of the sludge is further improved.
The invention has the beneficial effects that: compared with the prior art, the invention has the following advantages:
(1) the invention utilizes the thermal hydrolysis method coupled with the framework material method to carry out deep dehydration on the sludge, and the thermal hydrolysis method avoids the energy loss of latent heat of gasification brought away by the gasification of liquid water in the sludge, saves the energy consumption and reduces the operation cost.
(2) The invention utilizes the aminated Fenton carbon obtained by the hydro-thermal liquefaction of the Fenton iron mud as the framework material, thereby not only promoting the dehydration of the sludge, but also realizing the resource treatment of the Fenton iron mud.
(3) Due to the fact that hydrolysis of the sludge can be promoted under the alkaline condition, when ammonia water is used as a solvent to carry out hydrothermal liquefaction on Fenton iron mud, the skeleton material obtained after amination has amino groups, hydrolysis of extracellular polymers in the sludge can be effectively promoted, and the skeleton material has a catalytic hydrolysis function.
(4) The aminated Fenton carbon has a certain heat value, compared with other inorganic materials, the dehydrated sludge filter cake is used as a solid fuel, the heat value influence is small, the dehydrated sludge filter cake can be directly recycled and combusted, and the problem that inorganic substances are too much doped in the prior art and cannot be recycled is avoided.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1: under normal temperature and normal pressure, taking 20 g of Fenton iron mud with the water content of 55%, weighing 20 g of 28% ammonia water, stirring, adding the mixture into a hydrothermal reaction kettle, ensuring that the effective volume is below 80%, raising the temperature to 280 ℃ for hydrothermal liquefaction reaction, wherein the reaction time is 60min, washing and filtering the product with deionized water after the hydrothermal liquefaction reaction is finished, drying and grinding the product at 100 ℃ and sieving the product with a 100-mesh sieve to obtain the aminated Fenton carbon.
Taking 10 g of municipal sludge with the water content of 80% and 1.6 g of aminated Fenton carbon, uniformly stirring and adding the municipal sludge and the aminated Fenton carbon into a hydrothermal reaction kettle, ensuring that the effective volume is below 80%, raising the temperature to 160 ℃ and carrying out a thermal hydrolysis reaction, wherein the added water amount is 11.6 g, the reaction time is 90min, and after the thermal hydrolysis reaction is finished, carrying out vacuum filtration by using a vacuum pump to obtain a mud cake with the water content of 42% and filtrate.
Example 2: under normal temperature and normal pressure, 20 g of Fenton iron mud with the water content of 55 percent is taken, 10 g of 28 percent ammonia water is weighed, stirred and added into a hydrothermal reaction kettle, the effective volume is ensured to be below 80 percent, the temperature is raised to 300 ℃ for hydrothermal liquefaction reaction, the reaction time is 90min, after the hydrothermal liquefaction reaction is finished, deionized water is used for washing and filtering, and the obtained product is dried and ground at 100 ℃ and is sieved by a 300-mesh sieve to obtain the aminated Fenton carbon.
Taking 10 g of municipal sludge with the water content of 85 percent and 2.4 g of aminated Fenton carbon, uniformly stirring and adding the mixture into a hydrothermal reaction kettle, ensuring that the effective volume is below 80 percent, raising the temperature to 180 ℃ and carrying out a thermal hydrolysis reaction, wherein the added water amount is 6.2 g, the reaction time is 60min, and after the thermal hydrolysis reaction is finished, carrying out vacuum filtration by using a vacuum pump to obtain mud cakes with the water content of 39 percent and filtrate.
Example 3: taking 20 g of Fenton iron mud with the water content of 55% at normal temperature and normal pressure, weighing 30 g of water, stirring, adding the mixture into a hydrothermal reaction kettle, ensuring that the effective volume is below 80%, raising the temperature to 340 ℃ for hydrothermal liquefaction reaction, wherein the reaction time is 30min, washing and filtering the product with deionized water after the hydrothermal liquefaction reaction is finished, drying and grinding the product at 100 ℃ and sieving the product with a 200-mesh sieve to obtain the aminated Fenton carbon.
Taking 10 g of municipal sludge with the water content of 85 percent and 3.2 g of aminated Fenton carbon, uniformly stirring and adding the mixture into a hydrothermal reaction kettle, ensuring that the effective volume is below 80 percent, raising the temperature to 200 ℃ and carrying out a thermal hydrolysis liquefaction reaction, wherein the added water amount is 19.8 g, the reaction time is 30min, and after the thermal hydrolysis reaction is finished, carrying out vacuum filtration by using a vacuum pump to obtain a mud cake with the water content of 35 percent and filtrate.
Example 4: under normal temperature and normal pressure, taking 20 g of Fenton iron mud with the water content of 55%, weighing 20 g of 28% ammonia water, stirring, adding the mixture into a hydrothermal reaction kettle, ensuring that the effective volume is below 80%, raising the temperature to 280 ℃ for hydrothermal liquefaction reaction, wherein the reaction time is 60min, washing and filtering the product with deionized water after the hydrothermal liquefaction reaction is finished, drying at 100 ℃, grinding and sieving to obtain the aminated Fenton carbon.
Taking 10 g of municipal sludge with the water content of 80% and 1.6 g of aminated Fenton carbon, uniformly stirring and adding the municipal sludge and the aminated Fenton carbon into a hydrothermal reaction kettle, ensuring that the effective volume is below 80%, raising the temperature to 160 ℃ and carrying out a thermal hydrolysis reaction, wherein the added water amount is 11.6 g, the reaction time is 90min, and after the thermal hydrolysis reaction is finished, carrying out vacuum filtration by using a vacuum pump to obtain mud cakes with the water content of 44% and filtrate.
Example 5: under normal temperature and normal pressure, 20 g of Fenton iron mud with the water content of 55 percent is taken, 10 g of 28 percent ammonia water is weighed, stirred and added into a hydrothermal reaction kettle, the effective volume is ensured to be below 80 percent, the temperature is raised to 300 ℃ for hydrothermal liquefaction reaction, the reaction time is 90min, deionized water is used for washing and filtering after the hydrothermal liquefaction reaction is finished, and the aminated Fenton carbon is obtained by drying, grinding and sieving at 100 ℃.
Taking 10 g of municipal sludge with the water content of 84 percent and 2.4 g of aminated Fenton carbon, uniformly stirring and adding the municipal sludge and the aminated Fenton carbon into a hydrothermal reaction kettle, ensuring that the effective volume is below 80 percent, raising the temperature to 180 ℃ and carrying out a thermal hydrolysis reaction, wherein the added water amount is 12.4 g, the reaction time is 60min, and after the thermal hydrolysis reaction is finished, carrying out vacuum filtration by using a vacuum pump to obtain a mud cake with the water content of 40 percent and filtrate.
Example 6: under normal temperature and normal pressure, taking 20 g of Fenton iron mud with the water content of 55%, weighing 30 g of 28% ammonia water, stirring, adding the mixture into a hydrothermal reaction kettle, ensuring that the effective volume is below 80%, raising the temperature to 340 ℃ for hydrothermal liquefaction reaction, wherein the reaction time is 30min, washing and filtering the product with deionized water after the hydrothermal liquefaction reaction is finished, drying at 100 ℃, grinding and sieving to obtain the aminated Fenton carbon.
Taking 10 g of municipal sludge with the water content of 83 percent and 3.2 g of aminated Fenton carbon, uniformly stirring the municipal sludge and the aminated Fenton carbon, adding the mixture into a hydrothermal reaction kettle, ensuring that the effective volume is below 80 percent, raising the temperature to 200 ℃ and carrying out a thermal hydrolysis reaction, wherein the added water amount is 13.2 g, the reaction time is 60min, and carrying out vacuum filtration by using a vacuum pump after the thermal hydrolysis reaction is finished to obtain mud cakes with the water content of 36 percent and filtrate.
Comparison 1: taking 20 g of municipal sludge with the water content of 83% and 20 g of water, raising the temperature to 180 ℃, carrying out thermal hydrolysis reaction for 60min, and carrying out vacuum filtration by using a vacuum pump after the thermal hydrolysis reaction is finished to obtain a mud cake with the water content of 58% and a filtrate.
20 g of municipal sludge with the water content of 83% and 20 g of wood chips are taken, mixed and then mechanically pressed for 4 hours to obtain a mud cake with the water content of 55%.
Through detection, in the embodiments 1-6, the heat value of the aminated Fenton carbon is 8.92MJ/kg, and when the mass ratio of the 200 ℃ dry-based sludge to the aminated Fenton carbon is 1:1, the heat value of a filter cake is about 11.86MJ/kg, so that the recovery and utilization conditions are met.
Claims (5)
1. A method for deep dehydration of sludge by coupling a pyrohydrolysis technology with a framework material is characterized by comprising the following steps: deep dehydration is carried out on the sludge by a pyrohydrolysis technology and coupling of a framework material, and the method comprises the following steps:
(1) mixing sludge to be treated with the water content of 80-85% and aminated Fenton carbon serving as a framework material, and uniformly stirring to obtain a sludge mixture, wherein the mass ratio of dry-based sludge to the framework material is 1 (0.3-1.2); the Fenton iron mud is mud containing ferric iron obtained after a Fenton oxidation process in the sewage treatment process; the preparation method for preparing aminated Fenton carbon by carrying out hydrothermal liquefaction on Fenton iron mud comprises the following steps:
(1.1) mixing and uniformly stirring fenton iron mud and ammonia water, wherein the mass ratio of the fenton iron mud to the ammonia water is 1 (0.5-1.5);
(1.2) adding the mixture obtained in the step (1.1) into a hydrothermal reaction kettle, ensuring that the effective volume is below 80%, and then carrying out hydrothermal liquefaction reaction at the reaction temperature of 280-340 ℃ for 30-90 min;
(1.3) dehydrating the reaction product obtained in the step (1.2) to obtain filtrate and a solid product, washing the solid product with distilled water, drying at 100 ℃ for 24 hours, and grinding into powder;
(2) adding the sludge mixture obtained in the step (1) into a hydrothermal reaction kettle, and ensuring that the effective volume is below 80%, the hydrothermal liquefaction reaction temperature is 160-200 ℃, and the reaction time is 30-90 min;
(3) and (3) dehydrating the reaction product obtained in the step (2) to obtain filtrate and a dehydrated sludge filter cake.
2. The method for deep sludge dewatering by coupling the pyrohydrolysis technology with the framework material according to claim 1, wherein the framework material is aminated Fenton carbon obtained by hydrothermal liquefaction of Fenton iron mud.
3. The method for deep dehydration of sludge by coupling of pyrohydrolysis technology with framework material according to claim 2, characterized in that: the mass concentration of ammonia water in the step (1.1) is 28 percent.
4. The method for deep sludge dewatering by coupling the pyrohydrolysis technology with the framework material is characterized in that the mass ratio of the sludge mixture to the water in the step (2) is 1 (0.5-1.5).
5. The method for deep sludge dewatering by coupling the thermal hydrolysis technology with the framework material as claimed in claim 2, wherein the particle size of the aminated Fenton carbon after grinding and sieving is 100-300 mesh screen underflow.
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| CN112076723A (en) * | 2020-09-25 | 2020-12-15 | 南京理工大学 | Method for preparing heavy metal adsorbent by using Fenton sludge and application |
| CN112174455B (en) * | 2020-09-28 | 2022-10-28 | 江苏大学 | Method for deeply dehydrating sludge by using modified waste filter bag |
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Effective date of registration: 20221214 Address after: 710,018 Room 2006, Building A, Xinjie Community, Xi'an Economic and Technological Development Zone, Shaanxi Province Patentee after: Shaanxi Shanqin Energy Technology Service Co.,Ltd. Address before: 212013 No. 301, Xuefu Road, Zhenjiang, Jiangsu Patentee before: JIANGSU University |