CN115555012B - Method for preparing sludge-based catalyst by using petrochemical excess sludge and application - Google Patents
Method for preparing sludge-based catalyst by using petrochemical excess sludge and application Download PDFInfo
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- CN115555012B CN115555012B CN202211554359.4A CN202211554359A CN115555012B CN 115555012 B CN115555012 B CN 115555012B CN 202211554359 A CN202211554359 A CN 202211554359A CN 115555012 B CN115555012 B CN 115555012B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
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- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The invention discloses a method for preparing a sludge-based catalyst by utilizing petrochemical excess sludge and application thereof, wherein the preparation method comprises the following steps: s1: sludge pretreatment, S2: preparing a mixed solution, S3: drying and pyrolysis, S4: the invention takes pyrolysis temperature as a control factor, utilizes petrochemical surplus sludge to prepare Mn oxide-loaded catalysts at different temperatures, improves the catalysis efficiency and adsorption efficiency of the sludge-based catalyst by adding an activator, and simultaneously characterizes the prepared sludge-based catalyst to prove that the catalyst has higher specific surface area and pore volume and excellent adsorption and catalysis performances.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a method for preparing a sludge-based catalyst by utilizing petrochemical excess sludge and application thereof.
Background
The petrochemical industry is an important prop industry of national economy and plays an indispensable role in promoting the healthy development of national economy. At the same time, however, the petrochemical industry is one of the sources of hazardous waste, such as petrochemical sludge produced in the petrochemical industry production links.
Petrochemical sludge produced by a sewage treatment plant in the petrochemical industry in the processes of oil removal, air flotation, biological treatment and the like usually contains organic pollutants mainly comprising polychlorinated biphenyl PCBs (Polychlorinatedbiphenyls), polycyclic aromatic hydrocarbon PAHs (Polycyclicaromatichydrocarbons), phenols, benzene series and the like, heavy metals mainly comprising copper, mercury, chromium and the like, harmful microorganisms mainly comprising pathogenic bacteria and the like. On the one hand, petrochemical sludge treatment costs are high, and on the other hand, petrochemical sludge, if exposed to the environment for a long period of time, will cause serious pollution to the ecosystem. Efficient treatment of petrochemical sludge has thus become a significant challenge to the petrochemical industry. Meanwhile, the water quality components of the petrochemical wastewater are complex, and the treatment of the petrochemical wastewater is urgent due to toxicity and intractable property. Since 1984, the emission standards for petrochemical wastewater have been perfected. Most petrochemical wastewater treatment plants adopt a deep treatment process taking catalytic ozone oxidation as a core.
In recent years, catalytic ozonation technology has been widely used for wastewater treatment due to advantages of strong oxidizing ability, high efficiency and the like. The catalyst serves as one of the main units and functions to convert ozone into OH or enhance the ability to adsorb nucleophilic sites of molecules. Therefore, the choice of catalyst is critical to the catalytic ozonation system. The raw materials of the ozone catalyst are mainly transition metals or noble metals, and the preparation cost is high; the sludge is used as a natural carbon material and biomass resource, and the sludge biochar obtained by pyrolysis of the sludge can be used as an effective catalyst. However, the prior art utilizes sludge activated carbon SBAC to load MnO x And FeO x Respectively preparing MnO x SBAC and FeO x The characterization of SBAC reveals that both catalysts have reduced specific surface area, pore volume and average pore size with increasing temperature, probably due to the formation of metal oxides causing partial pore blockage.
The prior research finds that when the sludge activated carbon is loaded with metal oxide, the formed metal oxide can permeate and block the pores and channels of the activated carbon and also gather on the surface of the activated carbon; in addition, during the metal oxide loading process, the activated carbon may undergo secondary calcination, and the process may cause destruction of the structure of the activated carbon, resulting in further reduction of the specific surface area.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing a sludge-based catalyst by utilizing petrochemical excess sludge.
The technical scheme of the invention is as follows: a method for preparing a sludge-based catalyst by using petrochemical excess sludge, comprising the following steps:
s1, sludge pretreatment:
drying and crushing petrochemical excess sludge, and sieving to obtain sludge powder for later use;
s2, preparing a mixed solution:
adding sludge powder, mn salt and agar powder into ultrapure water according to a proportion, stirring for 0.5-2 hours, then adding ammonia water, and continuously stirring for 2-4 hours to obtain a mixed solution;
s3, drying and pyrolysis:
activating and drying the mixed solution to obtain a solid, placing the solid into a tube furnace, heating the solid in an inert gas atmosphere, keeping the temperature for 0.5-1.5 h after the temperature is raised to 500-800 ℃, and then cooling the solid to room temperature in the tube furnace;
s4, cooling and cleaning:
taking out the solid from the tube furnace, washing the solid with ethanol and ultrapure water for a plurality of times, drying, crushing and sieving the solid to obtain the sludge-based catalyst.
Further, the drying temperatures in the step S1 and the step S4 are 100-120 ℃, and the number of the sieving holes in the step S1 and the step S4 is 100 meshes.
Description: through setting up of stoving temperature, can make unnecessary moisture in the mud evaporate fast, through the setting of sieving for mud granule diminishes, thereby be convenient for petrochemical industry surplus sludge's further processing.
Further, the Mn salt in the step S2 is MnCl 2 The sludge powder and MnCl 2 The mass ratio of the agar powder to the agar powder is 0.9-1.5:0.8-1.2:0.8-1.2; the ratio of the sludge powder, the ultrapure water and the ammonia water is 1g:20mL:7mL.
Description: mn as a transition metal, manganese oxide as a strong catalyst for degrading ozone gas, and Mn of different valence states in liquid phase solution can cause metal oxide and O 3 Electron transfer occurs between them, thereby promoting the formation of OH; after carbonization of the agar powder, rich nucleophilic-CH organic functional groups are generated on the surface of the sludge,the dense pore channels on the surface of the sludge are combined with the organophilic functional groups, the specific surface area of the ceramic material is increased, the void structure is optimized, the organophilic property and the organic pollutant adsorption capacity of the sludge are increased, and the pollutant adsorption capacity and the catalyst loading performance and stability of the sludge-based catalyst can be further improved through different component proportions.
Further, as a preferred embodiment of the present invention, the activating method in step S3 is as follows: and (3) carrying out constant temperature treatment on the mixed solution in an oven for 2-3 hours at the temperature of 110-280 ℃ to obtain an activated solid.
Description: the petrochemical surplus sludge in the mixed liquid can be activated by heating and introducing air, and the specific surface area and the pore volume of the petrochemical surplus sludge can be increased.
Further, in the step S3, the inert gas is any one of helium, argon and neon, and the heating rate is 10 ℃/min.
Description: pyrolysis temperature is important for catalyst structure formation, and too fast a temperature increase may cause collapse of the catalyst carbon structure, and too slow a temperature increase is unfavorable for pore structure formation.
Further, as another preferable mode of the present invention, the step of activating in step S3 is:
s3-1, adding a primary activator into the mixed solution, and continuously stirring for 6-8 hours to perform primary activation; then, dehydrating and drying the mixed solution obtained after primary activation to obtain a dry solid;
s3-2, then placing the dried solid into a tube furnace, heating the dried solid from 25 ℃ at a heating rate of 8 ℃/min under the atmosphere of activated gas with constant concentration, uniformly spraying a secondary activator on the surface of the dried solid at an initial spraying rate of 0.15-0.2 ml/min, and adjusting the spraying rate of the secondary activator along with the temperature of the dried solid;
the spraying speed of the secondary activator is regulated according to the temperature of the dry solid, and the method comprises the following steps: before the temperature reaches 300-330 ℃, the spraying speed of the secondary activator increases by 0.01-0.015 ml/min along with 8 ℃ of each heating; after the temperature reaches 300-330 ℃, the spraying speed of the secondary activator is reduced by 0.02-0.03 ml/min along with 8 ℃ of each heating; stopping heating until the spraying speed of the secondary activator is zero, and then cooling to room temperature.
Description: through primary activation and secondary activation, the specific surface area and the pore volume of petrochemical excess sludge can be increased, and the adsorption effect of the prepared sludge-based catalyst is enhanced, and the catalytic effect is better; the mixed solution can be chemically activated by adding the primary activator, and CO can be generated by pyrolysis of the primary activator during secondary activation 2 Can further improve the surface structure of the catalyst, and can utilize CO by setting the spraying mode of the secondary activator 2 And the water generated in the spraying process is further physically activated, and meanwhile, the sludge is activated by using a physical and chemical method, so that the activation effect is optimal.
Further, the activated gas atmosphere has a volume concentration of 1.5-4.5% CO 2 The balance being inert gas and/or nitrogen; the constant concentration is specifically that activating gas atmosphere is injected circularly; and the gas concentration is monitored in real time and continuously regulated by a concentration detector.
Description: by CO 2 The pore structure of petrochemical excess sludge can be optimized, so that the adsorptivity of the prepared sludge-based catalyst is enhanced.
Further, the primary activator in the step S3 is 2-hydroxy ethylamine, KOH, znCl 2 0.5 to 0.8:1: mixing and preparing the materials according to a mass ratio of 0.5-0.8; the secondary activator is 2-hydroxy ethylamine, KOH, znCl 2 Ultrapure water was used as 1:0.5 to 0.8:0.2 to 0.5:10 mass ratio.
Description: k, zn formed during activation can be embedded in the sludge structure system in the form of oxides, thereby expanding the sludge and creating more pores, and KOH activation can form a narrower pore size distribution; the addition of the 2-hydroxy ethylamine can not only serve as an adhesive to improve the loading efficiency of the sludge-based catalyst, but also generate CO in the pyrolysis process 2 And (3) waiting for gas and improving the adsorption efficiency of the sludge-based catalyst.
Further, the invention also discloses a method for using the sludge-based catalyst in the catalytic ozone process of oxalic acid wastewater or in the catalytic ozone process of petrochemical wastewater; according to 1L oxalic acid wastewater/petrochemical wastewater: 1g of a sludge-based catalyst is added into oxalic acid wastewater/petrochemical wastewater in proportion; then, ozone with the flow rate of 300mL/min and the concentration of 33mg/L is introduced into the oxalic acid wastewater/petrochemical wastewater added with the sludge-based catalyst, and the mixture is stirred for 1h at room temperature, so that the catalysis is completed.
The beneficial effects of the invention are as follows:
(1) The preparation method of the invention prepares the Mn oxide-loaded catalyst by taking the pyrolysis temperature and the activator as control factors, and solves the problem of MnO loading in the prior study x The specific surface area, the pore volume and the average pore diameter of the catalyst are reduced along with the temperature rise;
(2) The invention can generate CO after primary activation by adding the primary activator and pyrolysis 2 Further improving the surface structure of the catalyst, and utilizing CO can be realized by setting the spraying mode of the secondary activator 2 The water generated in the spraying process is activated, and meanwhile, the sludge is activated by a physical and chemical method, so that the loading efficiency and the adsorption efficiency of the sludge-based catalyst are improved, the activation effect is better, and meanwhile, the prepared various sludge-based catalysts are characterized, so that the sludge-based catalyst has excellent catalysis and adsorption performances;
(3) According to the invention, the sludge-based catalyst is prepared by taking petrochemical excess sludge as a main raw material, and the purification treatment of petrochemical wastewater is performed by combining the sludge-based catalyst with ozone, so that the recycling of wastes is realized, the economical efficiency is achieved, the treatment effect is good, and the application prospect is wide.
Drawings
FIG. 1 is a SEM image at a magnification of 5000 times according to example 1 of the invention;
FIG. 2 is an SEM image at a magnification of 10000 times according to example 2 of the invention;
FIG. 3 is an SEM image at a magnification of 10000 times of example 3 of the invention;
FIG. 4 is an SEM image at a magnification of 10000 times of example 4 of the invention;
fig. 5 is an SEM image of comparative example 1 of the present invention at 10000 times enlarged.
Detailed Description
The invention will be described in further detail with reference to the following embodiments to better embody the advantages of the invention.
Example 1
A method for preparing a sludge-based catalyst by using petrochemical excess sludge, comprising the following steps:
s1, sludge pretreatment:
drying and crushing petrochemical excess sludge at 105 ℃, and sieving the crushed petrochemical excess sludge with a 100-mesh sieve to obtain sludge powder for later use;
s2, preparing a mixed solution:
10g of sludge powder and 10g of MnCl 2 Adding 10g of agar powder into 200ml of ultrapure water, stirring for 1h, then adding 70ml of ammonia water, and continuously stirring for 2.5h to obtain a mixed solution;
s3, drying and pyrolysis:
drying and activating the mixed solution in a drying oven at 220 ℃ for 3 hours to obtain activated solid, putting the solid into a tube furnace, heating the solid in a helium atmosphere at a heating rate of 10 ℃/min, keeping the temperature for 1 hour after the temperature is raised to 700 ℃, and then cooling the solid in the tube furnace to room temperature;
s4, cooling and cleaning:
taking out the solid from the tube furnace, washing the solid with ethanol and ultrapure water for three times, drying and crushing the solid at 105 ℃, and sieving the solid with a 100-mesh sieve to obtain the sludge-based catalyst.
Example 2
The difference between this example and example 1 is that the pyrolysis temperature in step S3 is different, and the temperature is kept for 0.5h after the temperature is raised to 500 ℃.
Example 3
The difference between this example and example 1 is that the pyrolysis temperature in step S3 is different, and the temperature is maintained for 0.8h after the temperature is raised to 600 ℃.
Example 4
The difference between this example and example 1 is that the pyrolysis temperature in step S3 is different, and the temperature is kept for 1.5 hours after the temperature is raised to 800 ℃.
Example 5
This example differs from example 1 in that 9g of sludge powder, 8g of MnCl are added 2 And 8g of agar powder are added into 180ml of ultrapure water and stirred for 0.5h, and then 63ml of ammonia water is added and stirring is continued for 4h, so as to obtain a mixed solution.
Example 6
This example differs from example 1 in that 15g of sludge powder, 12g of MnCl are added 2 And 12g of agar powder are added into 300ml of ultrapure water and stirred for 2 hours, and then 105ml of ammonia water is added for further stirring for 2 hours, so as to obtain a mixed solution.
Example 7
The difference between this embodiment and embodiment 1 is that the drying temperatures in step S1 and step S4 are 100 ℃.
Example 8
The difference between this embodiment and embodiment 1 is that the drying temperatures in step S1 and step S4 are 120 ℃.
Example 9
The present example differs from example 1 in that in step S3, the mixed solution is dried and activated in an oven at 110 ℃ for 2 hours to obtain an activated solid.
Example 10
This example differs from example 1 in that in step S3, the mixture is dried in an oven at 280 ℃ and activated for 3 hours to obtain an activated solid.
Example 11
The present embodiment is different from embodiment 1 in that the activation method in step S3 is different from the activation method in that:
s3-1, adding a primary activator into the mixed solution, and continuously stirring for 7 hours to perform primary activation; then, dehydrating and drying the mixed solution obtained after primary activation to obtain a dry solid; the primary activator is prepared from 2-hydroxy ethylamine, KOH and ZnCl 2 At 0.6:1:0.6 by mass ratio;
s3-2, then placing the dried solid into a tube furnace, and activating the gas atmosphere at a constant concentrationHeating the dried solid from 25 ℃ at a heating rate of 8 ℃/min, uniformly spraying the secondary activator on the surface of the dried solid at an initial spraying speed of 0.18ml/min, and adjusting the spraying speed of the secondary activator along with the temperature of the dried solid; the activated gas atmosphere is CO with volume concentration of 1.5% 2 Helium in balance;
the spraying speed of the secondary activator is regulated according to the temperature of the dry solid, and the method comprises the following steps: before the temperature reached 320 ℃, the spraying speed of the secondary activator increased by 0.013ml/min with each 8 ℃ rise in temperature; after the temperature reaches 320 ℃, the spraying speed of the secondary activator is reduced by 0.025ml/min with each heating up to 8 ℃; stopping heating until the spraying speed of the secondary activator is zero, and then cooling to room temperature; the secondary activator is prepared from 2-hydroxy ethylamine, KOH, znCl 2 Ultrapure water was used as 1:0.6:0.3:10 mass ratio.
Example 12
The difference between this example and example 11 is that the configuration components of the primary activator and the secondary activator in step S3-2 are different; the primary activator is 2-hydroxy ethylamine, KOH, znCl 2 At 0.5:1:0.5 mass ratio; the secondary activator is 2-hydroxy ethylamine, KOH and ZnCl 2 Ultrapure water was used as 1:0.5:0.2:10 mass ratio; .
Example 13
The difference between this example and example 11 is that the configuration components of the primary activator and the secondary activator in step S3-2 are different; the primary activator is 2-hydroxy ethylamine, KOH, znCl 2 At 0.8:1:0.8 by mass ratio; the secondary activator is 2-hydroxy ethylamine, KOH and ZnCl 2 Ultrapure water was used as 1:0.8:0.5:10 mass ratio.
Example 14
The difference between this example and example 11 is that step S3-1 is to add the primary activator to the mixture and continue stirring for 6 hours to perform the primary activation, wherein the activating gas atmosphere is CO with a volume concentration of 3.5% 2 The balance being nitrogenAnd (3) air.
Example 15
The difference between this example and example 11 is that step S3-1 is to add the primary activator to the mixture and continue stirring for 8 hours to perform the primary activation, wherein the activating gas atmosphere is CO with a volume concentration of 4.5% 2 The balance being nitrogen.
Example 16
This example differs from example 11 in that the initial rate of spraying of the secondary activator in step S3-2 is 0.15ml/min.
Example 17
This example differs from example 11 in that the initial rate of spraying of the secondary activator in step S3-2 is 0.2ml/min.
Example 18
This example differs from example 11 in that the spray rate of the secondary activator in step S3-2 was increased by 0.013ml/min with 8 ℃ per increase in temperature by the temperature at which the spray rate of the secondary activator was varied with dry solids until the temperature reached 300 ℃; after the temperature reached 300 ℃, the spraying rate of the secondary activator was reduced by 0.025ml/min with each 8 ℃ increase in temperature.
Example 19
This example differs from example 11 in that the spray rate of the secondary activator in step S3-2 was increased by 0.013ml/min with 8 ℃ per increase in temperature by the temperature at which the spray rate of the secondary activator varied with dry solids before the temperature reached 330 ℃; after the temperature reached 330 ℃, the spraying rate of the secondary activator was reduced by 0.025ml/min with each 8 ℃ increase in temperature.
Example 20
This example differs from example 11 in that the spray rate in step S3-2 is increased by a magnitude of 0.01ml/min with 8℃per increase in the spray rate of the secondary activator before the temperature reaches 320 ℃.
Example 21
This example differs from example 11 in that the spray rate in step S3-2 is increased by a magnitude of 0.015ml/min with 8℃per increase in the spray rate of the secondary activator before the temperature reaches 320 ℃.
Example 22
This example differs from example 11 in that the spray rate in step S3-2 is reduced in magnitude by 0.02ml/min for the spray rate of the secondary activator with 8℃per increase in temperature after the temperature reaches 320 ℃.
Example 23
This example differs from example 11 in that the spray rate in step S3-2 is reduced in magnitude by 0.03ml/min for the spray rate of the secondary activator with 8℃per increase in temperature after the temperature reaches 320 ℃.
Experimental example
Experiment one: the specific surface area and pore distribution influence of the sludge-based catalyst prepared in examples 1 to 23 is detected, and the influence of each parameter on the specific surface area and pore distribution of the sludge-based catalyst is analyzed, and the specific research is as follows:
1. the influence of different pyrolysis temperatures on the specific surface area and pore distribution of the prepared sludge-based catalyst is explored;
the results of the experiments are shown in the following table 1, with examples 1, 2, 3 and 4 as experimental comparisons:
TABLE 1 specific surface area and pore distribution of sludge-based catalysts at different pyrolysis temperatures
| Parameters (parameters) | Specific surface area (m) 2 /g） | Total pore volume (cm) 3 /g） | Average pore diameter (nm) |
| Example 1 | 175.83 | 0.173 | 4.92 |
| Example 2 | 173.88 | 0.062 | 3.07 |
| Example 3 | 174.80 | 0.168 | 3.45 |
| Example 4 | 159.79 | 0.187 | 5.66 |
As can be seen from table 1, the specific surface area and pore volume of the sludge-based catalyst tended to increase as the pyrolysis temperature increased from 500 ℃ to 700 ℃, with example 1 being optimal;
meanwhile, as the pyrolysis temperature increases, as shown in fig. 1, 2 and 3, the surface of the sludge-based catalyst shows a more developed pore structure; as shown in fig. 4, when the pyrolysis temperature was increased to 800 ℃, the total pore volume and the average pore diameter were increased in example 4, but the specific surface area thereof was decreased, resulting in a decrease in catalytic performance.
2. Exploring the influence of Mn salt addition on the specific surface area and pore distribution of the prepared sludge-based catalyst;
based on the mixed solution of example 1, a group of mixed solutions was set without adding Mn salt, and the remaining components were kept unchanged, which was designated as control example 1;
the results of the experiment were shown in Table 2 below, with example 1, comparative example 1 and example 5 being used as experimental comparisons:
TABLE 2 specific surface area and pore distribution of sludge-based catalysts at different mixture ratios
| Parameters (parameters) | Specific surface area (m) 2 /g） | Total pore volume (cm) 3 /g） | Average pore diameter (nm) |
| Example 1 | 175.83 | 0.173 | 4.92 |
| Example 5 | 169.43 | 0.168 | 4.52 |
| Comparative example 1 | 44.58 | 0.028 | 5.02 |
As can be seen from table 2, comparative example 1 has a less developed pore structure, a lower specific surface area and a lower total pore volume than example 1; as shown in FIG. 5, the surface of comparative example 1 was more hardened, and it was found that MnC was not added to the mixed solutionl 2 In this case, the specific surface area of the sludge-based catalyst is remarkably reduced.
3. Exploring the specific surface area and pore distribution condition of a sludge-based catalyst prepared at a drying temperature;
the results are shown in Table 3 below, with examples 1, 7 and 8 as experimental comparisons:
TABLE 3 specific surface area and pore distribution of sludge-based catalysts at different drying temperatures
| Parameters (parameters) | Specific surface area (m) 2 /g） | Total pore volume (cm) 3 /g） | Average pore diameter (nm) |
| Example 1 | 175.83 | 0.173 | 4.92 |
| Example 7 | 172.87 | 0.169 | 4.70 |
| Example 8 | 175.51 | 0.170 | 4.52 |
As can be seen from table 3, the specific surface area and the total pore volume of the sludge-based catalyst prepared under the conditions of example 8 are preferable for comparative example 7, but the increase in the stirring time and the drying temperature of the mixed liquor of example 8 of comparative example 1 has less influence on the specific surface area and the total pore volume of the sludge-based catalyst; therefore, example 1 is preferable.
4. Exploring the influence of the parameters of the first activation scheme on the specific surface area and pore distribution of the prepared sludge-based catalyst;
the results of the experiments are shown in the following table 4, with examples 1, 9 and 10 as experimental comparisons:
TABLE 4 specific surface area and pore distribution of sludge-based catalysts at different parameters of the first activation scheme
| Parameters (parameters) | Specific surface area (m) 2 /g） | Total pore volume (cm) 3 /g） | Average pore diameter (nm) |
| Example 1 | 175.83 | 0.173 | 4.92 |
| Example 9 | 171.54 | 0.162 | 4.56 |
| Example 10 | 175.94 | 0.171 | 4.61 |
As can be seen from Table 4, the specific surface area and the total pore volume of the catalyst obtained were increased by the increase in the activation temperature and the increase in the activation time, but the specific surface area was not significantly changed in example 10 as compared with example 1, but example 1 was preferable from the viewpoints of production cost and the like by using a higher activation temperature and activation time.
5. The influence of the component proportions of the primary activator and the secondary activator added in another activating scheme on the specific surface area and pore distribution of the prepared sludge-based catalyst is explored;
based on the primary activator and the secondary activator of example 11, no 2-hydroxyethylamine was added to the primary activator and the secondary activator, and the remaining components were kept unchanged, which was designated as control example 2;
the results of the experiments in comparison with control group 2, example 1, example 11, example 12 and example 13 are shown in table 5 below:
TABLE 5 specific surface area and pore distribution of sludge-based catalysts with the composition ratio of the primary activator and the secondary activator of another activation scheme
| Parameters (parameters) | Specific surface area (m) 2 /g） | Total pore volume (cm) 3 /g） | Average pore diameter (nm) |
| Example 1 | 175.83 | 0.173 | 4.92 |
| Example 11 | 196.65 | 0.187 | 4.71 |
| Example 12 | 194.93 | 0.167 | 4.69 |
| Example 13 | 194.79 | 0.171 | 4.59 |
| Comparative example 2 | 185.28 | 0.177 | 4.69 |
As can be seen from table 5, the activation of example 11 with the addition of the activator is better compared with the activation schemes of example 1 and example 11;
by comparing examples 11, 12 and 13, the ratio of the components in the primary activator and the ratio of the components in the secondary activator are changed, the specific surface area, the total pore volume and the average pore diameter are all affected, and example 11 is preferable; meanwhile, through the comparative example 11 and the comparative example 2, the specific surface area of the sludge-based catalyst prepared by the primary activator and the secondary activator is obviously reduced when the 2-hydroxy ethylamine is not added; in combination, example 11 is preferred.
6. Exploring the influence of the parameters of another activation scheme on the specific surface area and pore distribution of the prepared sludge-based catalyst;
the results of the experiments are shown in Table 6 below, with examples 11, 14 and 15 as experimental comparisons:
TABLE 6 specific surface area and pore distribution of sludge-based catalysts at different parameters for another activation scheme
| Parameters (parameters) | Specific surface area (m) 2 /g） | Total pore volume (cm) 3 /g） | Average pore diameter (nm) |
| Example 11 | 196.65 | 0.187 | 4.71 |
| Example 14 | 194.07 | 0.171 | 4.06 |
| Example 15 | 195.88 | 0.189 | 4.65 |
As can be seen from Table 6, the primary activator stirring time and CO content in the activated gas were increased by comparing examples 11, 14 and 15 2 The specific surface area and pore distribution of the sludge-based catalyst are both increased with CO 2 While the increase in the total pore volume of the sludge-based catalyst was still increasing but not significant, the specific surface area was decreased, and thus, overall, the parameters of example 11 were better.
7. The influence of a spraying mode of adding a secondary activating agent into another activating scheme on the specific surface area and pore distribution of the prepared sludge-based catalyst is explored;
comparative example 3 was set: heating the dried solid from 25 ℃ to 450 ℃ at a heating rate of 8 ℃/min, spraying a secondary activator on the surface of the dried solid at a spraying rate of 0.2ml/min, performing secondary activation on the dried solid, stopping heating at 450 ℃, and cooling to room temperature.
Comparative example 4 was set: heating the dried solid from 25 ℃ to 450 ℃ at a heating rate of 8 ℃/min, adjusting and spraying a secondary activator with an initial spraying speed of 0.18ml/min on the surface of the dried solid according to a spraying speed of 0.013ml/min increased every heating rate of 8 ℃, performing secondary activation on the dried solid, stopping heating at 450 ℃, and cooling to room temperature.
The results of the experimental comparisons were shown in the following table 7, with reference 3, reference 4, example 11, example 18 and example 19:
TABLE 7 specific surface area and pore distribution of sludge-based catalysts with the spraying of the secondary activator for the alternative activation scheme
| Parameters (parameters) | Specific surface area (m) 2 /g） | Total pore volume (cm) 3 /g） | Average pore diameter (nm) |
| Example 11 | 196.65 | 0.187 | 4.71 |
| Comparative example 3 | 189.85 | 0.157 | 4.15 |
| Comparative example 4 | 190.77 | 0.164 | 4.61 |
| Example 18 | 193.87 | 0.182 | 4.82 |
| Example 19 | 193.89 | 0.183 | 4.75 |
As can be seen from table 7, by comparing comparative example 3 and comparative example 4 with example 11, comparative example 3 was sprayed with a constant spraying speed, comparative example 4 was sprayed with a continuously increasing spraying speed, but the specific surface area of the sludge-based catalyst prepared in comparative example 3 and comparative example 4 was significantly reduced, and example 11 is preferable;
by comparing examples 18, 19 with example 11, the different temperature nodes of the spray rate switch have a certain effect on the specific surface area of the prepared sludge-based catalyst, with example 11 being preferred.
8. Exploring the influence of the spraying speed and the spraying speed change of the secondary activator added in another activating scheme on the specific surface area and pore distribution of the prepared sludge-based catalyst;
the results are shown in Table 8 below, with examples 11, 16, 17, 20, 21, 22 and 23 as experimental comparisons:
TABLE 8 specific surface area and pore distribution of sludge-based catalysts at different spray rates and different spray rates for secondary activators of alternative activation schemes
| Parameters (parameters) | Specific surface area (m) 2 /g） | Total pore volume (cm) 3 /g） | Average pore diameter (nm) |
| Example 11 | 196.65 | 0.187 | 4.71 |
| Example 16 | 193.62 | 0.180 | 4.93 |
| Example 17 | 193.45 | 0.183 | 4.86 |
| Example 20 | 194.03 | 0.178 | 4.93 |
| Example 21 | 194.10 | 0.177 | 4.86 |
| Example 22 | 194.21 | 0.179 | 4.83 |
| Example 23 | 195.61 | 0.185 | 4.79 |
As can be seen from Table 8, the specific surface area, the total pore volume and the average pore size of the spray rate all have an effect, and example 11 is preferred in the overall view;
by comparing example 11, example 20, example 21, example 22 and example 23, different rates of increase/decrease of the spraying speed have a certain effect on the specific surface area of the prepared sludge-based catalyst, wherein example 11 is preferred;
the effect of different initial spray rates on the sludge-based catalyst is evident by comparing example 11, example 16 and example 17, with example 11 being preferred.
Experiment II: in order to further compare the above examples, the following treatments were performed on the prepared oxalic acid solution and the sample of petrochemical wastewater collected from a petrochemical wastewater plant in Jilin city by using the sludge-based catalysts prepared in example 1, example 11, and comparative examples 1 to 4, respectively:
1. carrying out oxalic acid wastewater experiments by using the prepared sludge-based catalyst;
(1) The adsorption efficiency of the sludge-based catalyst is evaluated by utilizing an oxalic acid adsorption experiment of the sludge-based catalyst;
adding 1g/L of different types of sludge-based catalysts into oxalic acid with initial concentration of 100mg/L for adsorption treatment experiments, introducing oxygen with flow rate of 300mL/min, stirring at room temperature, and removing oxalic acid and TOC at 60min as shown in Table 9:
table 9 oxalic acid removal TOC removal by adsorption of oxalic acid with sludge-based catalyst
| Group of | Oxalic acid removal rate | TOC removal rate |
| Example 1 | 81.24% | 77.88% |
| Comparative example 1 | 18.06% | 4.87% |
| Comparative example 2 | 83.77% | 76.83% |
| Comparative example 3 | 85.65% | 80.14% |
| Comparative example 4 | 85.77% | 80.83% |
| Example 11 | 89.86% | 80.63% |
As can be seen from table 9, example 11 had the best effect on oxalic acid adsorption removal and the highest adsorption efficiency; and the oxalic acid removal rate and TOC removal rate of comparative example 1 without Mn salt are the lowest;
(2) An experiment of catalyzing oxalic acid by using a sludge-based catalyst to treat the oxalic acid is utilized to evaluate the catalysis effect of the sludge-based catalyst;
comparative example 5: without adding a sludge-based catalyst, only 300mL/min and 33mg/L of ozone are introduced into oxalic acid with initial concentration of 100mg/L, and stirring is carried out at room temperature;
experimental example: adding 1g/L of different types of sludge-based catalysts into oxalic acid with initial concentration of 100mg/L for catalytic ozone oxidation treatment experiment, introducing ozone with flow rate of 300mL/min and concentration of 33mg/L, adding 100mg/L of tertiary butanol and p-benzoquinone with concentration of all, stirring at room temperature,
oxalic acid removal and TOC removal at 20min are shown in table 10:
table 10 experiment of sludge-based catalyst to catalyze oxalic acid for 20min oxalic acid removal TOC removal
| Group of | Oxalic acid removal rate | TOC removal rate |
| Example 1 | 96.92% | 92.52% |
| Comparative example 1 | 19.75% | 10.12% |
| Comparative example 2 | 97.17% | 86.63% |
| Comparative example 3 | 98.06% | 93.65% |
| Comparative example 4 | 98.64% | 93.99% |
| Comparative example 5 | 19.27% | 10.24% |
| Example 11 | 99.89% | 95.56% |
Oxalic acid removal and TOC removal at 60min are shown in table 11:
table 11 experiment of sludge-based catalyst to catalyze oxalic acid 60min oxalic acid removal TOC removal
| Group of | Oxalic acid removal rate | TOC removal rate |
| Example 1 | 99.19% | 95.71% |
| Comparative example 1 | 35.72% | 38.35% |
| Comparative example 2 | 99.43% | 94.33% |
| Comparative example 3 | 99.78% | 95.75% |
| Comparative example 4 | 99.77% | 94.84% |
| Comparative example 5 | 32.59% | 33.13% |
| Example 11 | 99.89% | 98.63% |
As can be seen from tables 10 and 11, at 20min, the oxalic acid is almost completely removed at 20min in example 11, and the oxalic acid removal rate in the system for degrading oxalic acid by catalytic ozonation by the sludge-based catalyst prepared in each group of examples is gradually increased with the increase of the pyrolysis temperature at 60 min; example 11 was selected as optimal considering the economy of preparing the sludge-based catalyst;
moreover, it can be seen that the capacity of the sludge-based catalyst prepared in example 11 to catalyze ozone to treat oxalic acid and TOC is much higher than that of comparative example 1 and comparative example 5.
2. Carrying out petrochemical wastewater experiments by using the prepared sludge-based catalyst;
the method comprises the steps of utilizing a sludge-based catalyst to catalyze an experiment of ozone treatment petrochemical wastewater to evaluate the adsorption efficiency and the catalysis efficiency of the sludge-based catalyst;
experimental example: 1g of the sludge-based catalyst of example 1 and the sludge-based catalyst of example 11 are respectively added into 1L of petrochemical wastewater, 24mg/L of ozone is introduced at 300mL/min, 100mg/L of tertiary butanol and p-benzoquinone with the concentrations of both are added, and stirring is carried out at room temperature; obtaining petrochemical wastewater after catalytic purification;
comparative example 6: adding 1g of the sludge-based catalyst obtained in the example 1 into 1L of petrochemical wastewater, introducing oxygen at a rate of 300mL/min, and stirring at room temperature; obtaining petrochemical wastewater after catalytic purification;
comparative example 7: adding 1g of the sludge-based catalyst obtained in example 11 into 1L of petrochemical wastewater, introducing oxygen at a rate of 300mL/min, and stirring at room temperature; obtaining petrochemical wastewater after catalytic purification;
comparative example 8: the sludge-based catalyst is not added, and only 300mL/min and 24mg/L of ozone are introduced into 1L of petrochemical wastewater; stirring at room temperature; obtaining petrochemical wastewater after catalytic purification;
TOC removal UV at 30min 254 The removal rates are as in table 12:
table 12 experiment of sludge-based catalyst catalysis/adsorption petrochemical wastewater 30minTOC removal UV 254 Removal rate of
| Group of | TOC removal rate | UV 254 Removal rate of |
| Example 1 | 60.64% | 89.07% |
| Example 11 | 86.96% | 91.29% |
| Comparative example 1 | 17.37% | 75.02% |
| Comparative example 2 | 75.79% | 89.96% |
| Comparative example 3 | 76.52% | 90.02% |
| Comparative example 4 | 78.68% | 89.87% |
| Comparative example 6 | 54.14% | 81.78% |
| Comparative example 7 | 68.49% | 88.15% |
| Comparative example 8 | 16.37% | 72.02% |
As can be seen from Table 12, after the reaction was carried out for 30 minutes, the catalytic ozone treatment efficiency was obtained in comparative example 1, comparative example 6, and comparative example 8>Adsorption treatment efficiency>The efficiency of ozone treatment alone, comparative examples 6, 1 and 11, demonstrate TOC removal and UV after addition of sludge-based catalyst 254 The removal rate was increased, with example 11 being optimal;
meanwhile, the removal effect of each of comparative example 2, comparative example 3 and comparative example 4 was improved as compared with example 1.
Claims (8)
1. A method for preparing a sludge-based catalyst by using petrochemical excess sludge, which is characterized by comprising the following steps:
s1, sludge pretreatment:
drying and crushing petrochemical excess sludge, and sieving to obtain sludge powder for later use;
s2, preparing a mixed solution:
adding sludge powder, mn salt and agar powder into ultrapure water according to a proportion, stirring for 0.5-2 hours, then adding ammonia water, and continuously stirring for 2-4 hours to obtain a mixed solution;
s3, drying and pyrolysis:
activating and drying the mixed solution to obtain a solid, placing the solid into a tube furnace, heating the solid in an inert gas atmosphere, keeping the temperature for 0.5-1.5 h after the temperature is raised to 500-800 ℃, and then cooling the solid to room temperature in the tube furnace;
s4, cooling and cleaning:
taking out the solid from the tube furnace, washing the solid with ethanol and ultrapure water for a plurality of times, drying, crushing and sieving to obtain a sludge-based catalyst;
the activation method in the step S3 is as follows:
s3-1, adding a primary activator into the mixed solution, and continuously stirring for 6-8 hours to perform primary activation; then, dehydrating and drying the mixed solution obtained after primary activation to obtain a dry solid;
s3-2, then placing the dried solid into a tube furnace, heating the dried solid from 25 ℃ at a heating rate of 8 ℃/min under the atmosphere of activated gas with constant concentration, uniformly spraying a secondary activator on the surface of the dried solid at an initial spraying rate of 0.15-0.2 ml/min, and adjusting the spraying rate of the secondary activator along with the temperature of the dried solid;
the spraying speed of the secondary activator is regulated according to the temperature of the dry solid, and the method comprises the following steps: before the temperature reaches 300-330 ℃, the spraying speed of the secondary activator increases by 0.01-0.015 ml/min along with 8 ℃ of each heating; after the temperature reaches 300-330 ℃, the spraying speed of the secondary activator is reduced by 0.02-0.03 ml/min along with 8 ℃ of each heating; stopping heating until the spraying speed of the secondary activator is zero, and then cooling to room temperature.
2. The method for preparing a sludge-based catalyst by using petrochemical excess sludge according to claim 1, wherein the drying temperature in the step S1 and the step S4 is 100-120 ℃, and the number of the sieve holes sieved in the step S1 and the step S4 is 100 mesh.
3. The method for preparing a sludge-based catalyst using petrochemical excess sludge according to claim 1, wherein the Mn salt in step S2 is MnCl 2 The sludge powder、MnCl 2 The mass ratio of the agar powder to the agar powder is 0.9-1.5:0.8-1.2:0.8-1.2; the ratio of the sludge powder, the ultrapure water and the ammonia water is 1g:20mL:7mL.
4. A method for preparing a sludge-based catalyst using petrochemical excess sludge according to claim 1, wherein the method of activation in step S3 is: and (3) carrying out constant temperature treatment on the mixed solution in an oven for 2-3 hours at the temperature of 110-280 ℃ to obtain an activated solid.
5. The method for preparing a sludge-based catalyst using petrochemical excess sludge according to claim 1, wherein the inert gas in step S3 is any one of helium, argon and neon, and the temperature rising rate is 10 ℃/min.
6. The method for preparing a sludge-based catalyst by using petrochemical excess sludge according to claim 1, wherein the activated gas atmosphere has a volume concentration of 1.5-4.5% co 2 The balance being inert gas and/or nitrogen.
7. The method for preparing sludge-based catalyst by utilizing petrochemical excess sludge according to claim 1, wherein the primary activator in the step S3 is 2-hydroxyethylamine, KOH, znCl 2 0.5 to 0.8:1: mixing and preparing the materials according to a mass ratio of 0.5-0.8; the secondary activator is 2-hydroxy ethylamine, KOH, znCl 2 Ultrapure water was used as 1:0.5 to 0.8:0.2 to 0.5:10 mass ratio.
8. The application of the sludge-based catalyst prepared by the method for preparing the sludge-based catalyst by utilizing petrochemical excess sludge according to any one of claims 1-7, wherein the sludge-based catalyst is applied to a catalytic ozone process of oxalic acid wastewater or a catalytic ozone process of petrochemical wastewater.
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