CN115555012A - Method for preparing sludge-based catalyst by utilizing petrochemical excess sludge and application - Google Patents

Method for preparing sludge-based catalyst by utilizing petrochemical excess sludge and application Download PDF

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CN115555012A
CN115555012A CN202211554359.4A CN202211554359A CN115555012A CN 115555012 A CN115555012 A CN 115555012A CN 202211554359 A CN202211554359 A CN 202211554359A CN 115555012 A CN115555012 A CN 115555012A
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sludge
based catalyst
petrochemical
solid
temperature
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CN115555012B (en
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付丽亚
吴昌永
齐月
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Chinese Research Academy of Environmental Sciences
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Chinese Research Academy of Environmental Sciences
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    • 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
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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 pyrolyzing, S4: the preparation method comprises the steps of cooling and cleaning, wherein pyrolysis temperature is used as a control factor, the Mn oxide-loaded catalyst is prepared from petrochemical excess sludge at different temperatures, the catalytic efficiency and the adsorption efficiency of the sludge-based catalyst are improved by adding an activating agent, and the prepared sludge-based catalyst is characterized and proved to have higher specific surface area and pore volume and excellent adsorption and catalytic performances.

Description

Method for preparing sludge-based catalyst by utilizing petrochemical excess sludge and application
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 supporting industry of national economy and plays an indispensable role in promoting the healthy development of national economy. Meanwhile, the petrochemical industry is one of the sources for generating dangerous waste, such as petrochemical sludge generated in the production link of the petrochemical industry.
Petrochemical sludge produced in oil removal, air flotation, biological treatment and other processes of sewage treatment plants in the petrochemical industry generally contains organic pollutants mainly comprising polychlorinated biphenyl (PCBs), polycyclic Aromatic Hydrocarbons (PAHs), 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 one hand, petrochemical sludge has high treatment cost, and on the other hand, the petrochemical sludge can cause serious pollution to an ecological system if being exposed in the environment for a long time. Efficient disposal of petrochemical sludge has thus become a major challenge for the petrochemical industry. Meanwhile, the water quality of the petrochemical wastewater is complex, and the treatment of the petrochemical wastewater is urgent due to the toxicity and the stubborn property of the petrochemical wastewater. The discharge standard of petrochemical wastewater is continuously perfected from 1984. Most of the petrochemical sewage treatment plants adopt an advanced treatment process taking catalytic ozonation as a core.
In recent years, catalytic ozonation technology has been widely used for wastewater treatment due to its advantages of strong oxidation ability, high efficiency, etc. The catalyst serves as one of the main units, and functions to convert ozone to 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 material of the ozone catalyst is mainly oneThe transition metal or the noble metal has higher preparation cost; the sludge is used as a resource of carbon materials and biomass in nature, and the sludge biochar after pyrolysis can be used as an effective catalyst. However, in the prior art, the sludge activated carbon SBAC is used for loading MnO x And FeO x Respectively prepare MnO x SBAC and FeO x The characterization of the catalyst shows that the specific surface area, the pore volume and the average pore diameter of the two catalysts are reduced along with the increase of the temperature, and the formed metal oxide can cause partial pore blockage.
The existing research finds that when the sludge activated carbon is loaded with metal oxides, the formed metal oxides can permeate and block pores and channels of the activated carbon and can be gathered on the surface of the activated carbon; in addition, during the metal oxide supporting process, the activated carbon may be subjected to secondary calcination, and the process may cause structural destruction 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 utilizing petrochemical excess sludge comprises 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 the sludge powder, the Mn salt and the agar powder into ultrapure water according to a proportion, stirring for 0.5 to 2h, then adding ammonia water, and continuously stirring for 2 to 4h to obtain a mixed solution;
s3, drying and pyrolyzing:
activating and drying the mixed solution to obtain a solid, putting the solid into a tubular furnace, heating the solid in an inert gas atmosphere to 500-800 ℃, keeping the temperature for 0.5-1.5 h, and then cooling the solid to room temperature in the tubular furnace;
s4, cooling and cleaning:
and taking out the solid from the tubular furnace, washing the solid for multiple times by using ethanol and ultrapure water, drying and crushing the solid, and sieving the solid to obtain the sludge-based catalyst.
Further, the drying temperature in the step S1 and the step S4 is 100 to 120 ℃, and the number of the sieve holes sieved in the step S1 and the step S4 is 100 meshes.
Description of the drawings: through the setting of stoving temperature, can be so that unnecessary moisture rapid evaporation in the mud for the mud granule diminishes through the setting that sieves, thereby is convenient for the further processing of petrochemical industry excess sludge.
Further, the Mn salt in the step S2 is MnCl 2 Said sludge powder, mnCl 2 And the mass ratio of the agar powder to the agar powder is 0.9 to 1.5, and 0.8 to 1.2; the proportion of sludge powder, ultrapure water and ammonia water is 1g.
Description of the drawings: mn is used as a transition metal, manganese oxide is a strong catalyst for degrading ozone gas, and in a liquid phase solution, mn with different valence states can cause metal oxide and O 3 Electron transfer occurs between the two, thereby promoting the formation of OH; abundant pro-CH organic functional groups are generated on the surface of the sludge after the agar powder is carbonized, dense pore channels on the surface of the sludge are combined with the pro-CH organic functional groups, the specific surface area of the ceramic-based material is increased, the gap structure is optimized, the organophile and organic pollutant adsorption capacity of the sludge are increased, and the adsorption capacity, catalyst loading performance and stability of sludge-based catalyst pollutants can be further improved through different component proportion.
Further, as a preferable embodiment of the present invention, the activation method in step S3 is: and (3) treating the mixed solution in an oven at a constant temperature of 110-280 ℃ for 2-3 h to obtain an activated solid.
Description of the drawings: the petrochemical excess sludge in the mixed liquid can be activated by heating and introducing air, and the specific surface area and the pore volume of the mixed liquid can be increased.
Further, in the step S3, the inert gas is any one of helium, argon and neon, and the temperature rise rate is 10 ℃/min.
Description of the drawings: pyrolysis temperature is important for catalyst structure formation, and too fast temperature increase may cause collapse of the catalyst carbon structure, and too slow temperature increase is not favorable for pore structure formation.
Further, as another preferable embodiment of the present invention, the step of activating in step S3 is:
s3-1, adding a primary activating agent into the mixed solution, and continuously stirring for 6 to 8h for primary activation; then dehydrating and drying the mixed solution obtained after the primary activation to obtain a dry solid;
s3-2, putting the dry solid into a tubular furnace, heating the dry solid from 25 ℃ at a heating rate of 8 ℃/min under an activated gas atmosphere with constant concentration, uniformly spraying a secondary activating agent on the surface of the dry solid at an initial spraying speed of 0.15 to 0.2ml/min, wherein the spraying speed of the secondary activating agent is adjusted along with the temperature of the dry solid;
the spraying speed of the secondary activator is adjusted along with the temperature of the dry solid by the following method: before the temperature reaches 300 to 330 ℃, the spraying speed of the secondary activator is increased by 0.01 to 0.015ml/min along with the temperature rise of 8 ℃; after the temperature reaches 300 to 330 ℃, the spraying speed of the secondary activator is reduced by 0.02 to 0.03ml/min along with the temperature rise of 8 ℃; and stopping heating until the spraying speed of the secondary activating agent is zero, and then cooling to room temperature.
Description of the drawings: the specific surface area and the pore volume of the petrochemical excess sludge can be increased through primary activation and secondary activation, and the adsorption effect of the prepared sludge-based catalyst is enhanced, so that the catalytic effect is better; the mixed liquid can be chemically activated by adding the first-stage activating agent, and CO can be generated by pyrolyzing the first-stage activating agent during secondary activation 2 The surface structure of the catalyst can be further improved, and CO can be utilized by the arrangement of the spraying mode of the secondary activating agent 2 And the water generated in the spraying process is further physically activated, and the sludge is activated by utilizing physical and chemical methods, so that the activation effect is optimal.
Further, the activated gas atmosphere contains 1.5 to 4.5% by volume of CO 2 The balance of inert gas and/or nitrogen; the constant concentration is specifically the atmosphere of circularly injected activated gas; and is real-time detected by a concentration detectorThe gas concentration was monitored and continuously adjusted.
Description of the drawings: by CO 2 The pore structure of the petrochemical excess sludge can be optimized, so that the adsorptivity of the prepared sludge-based catalyst is enhanced.
Further, the first-stage activating agent in the step S3 is 2-hydroxyethylamine, KOH, znCl 2 And (2) the ratio of (1) to (2) is 0.5 to 0.8:1:0.5 to 0.8 in mass ratio; the second-stage activator is 2-hydroxyethylamine, KOH and ZnCl 2 And ultrapure water in a ratio of 1:0.5 to 0.8:0.2 to 0.5:10 by mass ratio.
Description of the drawings: k and Zn formed in the activation process can be embedded into a sludge structural system in an oxide form, so that the sludge is expanded and more pores are generated, and the KOH activation can form narrower pore size distribution; the 2-hydroxyethylamine is added, so that the effect of serving as a binder is improved, the loading efficiency of the sludge-based catalyst is improved, and CO can be generated in the pyrolysis process 2 And the gas is used for improving the adsorption efficiency of the sludge-based catalyst.
Furthermore, the invention also discloses the application of the sludge-based catalyst in the catalytic ozone process of oxalic acid wastewater or the catalytic ozone process of petrochemical wastewater; according to 1L of oxalic acid wastewater/petrochemical wastewater: 1g of sludge-based catalyst, adding the sludge-based catalyst into the oxalic acid wastewater/petrochemical wastewater; 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 to complete the catalysis.
The beneficial effects of the invention are:
(1) The preparation method of the invention prepares the Mn oxide-loaded catalyst by taking pyrolysis temperature and activating agent as control factors, thereby solving the problem of MnO loading in the existing research x The specific surface area, the pore volume and the average pore diameter of the catalyst are all reduced along with the temperature rise;
(2) By adding the first-stage activating agent, the invention can generate CO by pyrolysis after one-time activation 2 Further improve the surface structure of the catalyst, and can utilize CO by arranging the spraying mode of the secondary activating agent 2 And sprayed overThe water generated in the process is activated, and simultaneously, the sludge is activated by utilizing 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 and proved to have excellent catalysis and adsorption properties;
(3) The sludge-based catalyst is prepared by taking the petrochemical excess sludge as a main raw material, and the sludge-based catalyst is combined with ozone to purify the petrochemical wastewater, so that the waste recycling is realized, the economical efficiency is considered, the good treatment effect is achieved, and the wide application prospect is realized.
Drawings
FIG. 1 is a 5000-fold magnified SEM image of example 1 of the present invention;
FIG. 2 is an SEM image of example 2 of the present invention at magnification of 10000 times;
FIG. 3 is an SEM image of example 3 of the present invention magnified 10000 times;
FIG. 4 is an SEM photograph of example 4 of the present invention magnified 10000 times;
FIG. 5 is an SEM photograph of comparative example 1 of the present invention magnified 10000 times.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments thereof for better understanding the advantages of the invention.
Example 1
A method for preparing a sludge-based catalyst by utilizing petrochemical excess sludge comprises the following steps:
s1, sludge pretreatment:
drying the petrochemical excess sludge at 105 ℃, crushing, and sieving with a 100-mesh sieve to obtain sludge powder for later use;
s2, preparing a mixed solution:
mixing 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 pyrolyzing:
drying and activating the mixed solution in an oven at 220 ℃ for 3h to obtain an activated solid, putting the solid into a tubular furnace, heating at a heating rate of 10 ℃/min in a helium atmosphere, keeping the temperature for 1h after heating to 700 ℃, and then cooling the solid to room temperature in the tubular furnace;
s4, cooling and cleaning:
and taking out the solid from the tubular 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 temperature in step S3 is different, and after the temperature is raised to 500 ℃, the temperature is maintained for 0.5h.
Example 3
The difference between this example and example 1 is that the 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 temperature in step S3 is different, and the temperature is maintained for 1.5h after the temperature is raised to 800 ℃.
Example 5
The present example is different from example 1 in that 9g of sludge powder and 8g of MnCl were mixed 2 And 8g of agar powder are added into 180ml of ultrapure water and stirred for 0.5h, then 63ml of ammonia water is added and stirring is continued for 4h, and mixed liquid is obtained.
Example 6
This example is different from example 1 in that 15g of sludge powder and 12g of MnCl were mixed 2 And 12g of agar powder are added into 300ml of ultrapure water and stirred for 2 hours, then 105ml of ammonia water is added and stirring is continued for 2 hours, and mixed liquor is obtained.
Example 7
The present embodiment is different from embodiment 1 in that the drying temperature in step S1 and step S4 is 100 ℃.
Example 8
The difference between this embodiment and embodiment 1 is that the drying temperature in step S1 and step S4 is 120 ℃.
Example 9
The difference between this example and example 1 is that in step S3, the mixed solution is dried and activated for 2 hours at 110 ℃ in an oven to obtain an activated solid.
Example 10
The difference between this example and example 1 is that in step S3, the mixed solution is dried in an oven at 280 ℃ and activated for 3 hours to obtain an activated solid.
Example 11
The present example is different from example 1 in that the activation method in step S3 is different, and the activation method is:
s3-1, adding a primary activating agent into the mixed solution, and continuously stirring for 7 hours to carry out primary activation; then dehydrating and drying the mixed solution obtained after the primary activation to obtain a dry solid; the first-stage activator is prepared from 2-hydroxyethylamine, KOH and ZnCl 2 Mixing the components in a ratio of 0.6:1:0.6 by mass ratio;
s3-2, then putting the dried solid into a tubular furnace, heating the dried solid from 25 ℃ at a heating rate of 8 ℃/min under an activated gas atmosphere with constant concentration, uniformly spraying a secondary activating agent on the surface of the dried solid at an initial spraying speed of 0.18ml/min, wherein the spraying speed of the secondary activating agent is adjusted along with the temperature of the dried solid; the activated gas atmosphere is CO with the volume concentration of 1.5 percent 2 The balance being helium;
the spraying speed of the secondary activator is adjusted along with the temperature of the dry solid by the following method: before the temperature reaches 320 ℃, the spraying speed of the secondary activating agent is increased by 0.013ml/min along with the increase of 8 ℃ per temperature rise; after the temperature reaches 320 ℃, the spraying speed of the secondary activator is reduced by 0.025ml/min along with the increase of 8 ℃ per temperature; stopping heating until the spraying speed of the secondary activating agent is zero, and then cooling to room temperature; the secondary activator is 2-hydroxyethylamine, KOH or ZnCl 2 And ultrapure water in a ratio of 1:0.6:0.3:10 by mass ratio.
Example 12
This example is different from example 11 in that the configuration components of the primary activator and the secondary activator in step S3-2 are different; the first-stage activator is 2-hydroxyethylamine, KOH, znCl 2 Mixing the components in a ratio of 0.5:1:0.5 by mass ratio; the second-stage activator is 2-hydroxyethylamine, KOH, znCl 2 And ultrapure water in a ratio of 1:0.5:0.2:10 in a mass ratio; .
Example 13
This example is different from example 11 in that the configuration components of the primary activator and the secondary activator in step S3-2 are different; the first-stage activator is 2-hydroxyethylamine, KOH, znCl 2 And (3) adding the following components in a ratio of 0.8:1:0.8, and mixing and preparing; the second-stage activator is 2-hydroxyethylamine, KOH, znCl 2 And ultrapure water in a ratio of 1:0.8:0.5:10 by mass ratio.
Example 14
This example is different from example 11 in that step S3-1 is a step of adding a primary activating agent to the mixed solution and continuing to stir for 6 hours for primary activation, and the activating gas atmosphere is CO with a volume concentration of 3.5% 2 And the balance being nitrogen.
Example 15
This example is different from example 11 in that step S3-1 is to add a primary activating agent to the mixed solution and to continue stirring for 8 hours for primary activation, and the activating gas atmosphere is 4.5% by volume CO 2 And 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 is different from example 11 in that the initial speed of spraying the secondary activator in step S3-2 was 0.2ml/min.
Example 18
This example is different from example 11 in that the spraying speed of the secondary activator in step S3-2 was changed with the dry solid at a temperature at which the spraying speed was increased by 0.013ml/min with each temperature rise of 8 ℃ until the temperature reached 300 ℃; after the temperature reached 300 ℃, the spraying rate of the secondary activator decreased by 0.025ml/min with each 8 ℃ increase in temperature.
Example 19
This example is different from example 11 in that the temperature at which the spraying speed of the secondary activator is varied with the dried solid in step S3-2 is such that the spraying speed of the secondary activator is increased by 0.013ml/min with 8 ℃ per temperature rise before the temperature reaches 330 ℃; after the temperature reached 330 ℃, the spraying rate of the secondary activator decreased by 0.025ml/min with each 8 ℃ increase in temperature.
Example 20
This example is different from example 11 in that the spraying speed in step S3-2 is increased by 0.01ml/min at 8 ℃ per temperature rise until the temperature reaches 320 ℃.
Example 21
This example is different from example 11 in that the spraying speed in step S3-2 was increased by 0.015ml/min with an increase in spraying speed per 8 ℃ temperature rise until the temperature reached 320 ℃.
Example 22
This example is different from example 11 in that the spraying speed in step S3-2 is reduced by 0.02ml/min with a spraying speed of the secondary activator reduced with 8 ℃ per temperature rise after the temperature reached 320 ℃.
Example 23
This example is different from example 11 in that the spraying speed in step S3-2 is reduced by 0.03ml/min with a spraying speed of the secondary activator reduced with 8 ℃ per temperature rise after the temperature reached 320 ℃.
Examples of the experiments
Experiment one: now, the impact of the specific surface area and the pore distribution of the sludge-based catalyst prepared in examples 1 to 23 is detected to analyze the impact of each parameter on the specific surface area and the pore distribution of the sludge-based catalyst, and the following specific researches are carried out:
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 experimental comparisons of example 1, example 2, example 3, and example 4 are shown in table 1 below:
TABLE 1 specific surface area and pore distribution of sludge-based catalysts at different pyrolysis temperatures
Parameter(s) 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 tend to increase as the pyrolysis temperature increases from 500 ℃ to 700 ℃, with example 1 being the most preferred;
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 ℃, although the total pore volume and the average pore diameter were increased, the specific surface area was decreased, resulting in a decrease in catalytic performance in example 4.
2. The influence of the addition of Mn salt on the specific surface area and pore distribution of the prepared sludge-based catalyst is explored;
taking the mixed solution of the embodiment 1 as a reference, setting a group of mixed solutions without adding Mn salt, and keeping the other components unchanged, and recording as a comparative example 1;
the results of experimental comparisons of example 1, comparative example 1 and example 5 are shown in table 2 below:
TABLE 2 specific surface area and pore distribution of sludge-based catalysts at different mixture ratios
Parameter(s) 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 MnCl was not added to the liquid mixture 2 In this case, the specific surface area of the sludge-based catalyst is significantly reduced.
3. The specific surface area and pore distribution condition of the sludge-based catalyst prepared at the drying temperature are explored;
the results of experimental comparisons of example 1, example 7 and example 8 are shown in table 3 below:
TABLE 3 specific surface area and pore distribution of sludge-based catalysts at different drying temperatures
Parameter(s) 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, in comparative example 7, the specific surface area and total pore volume of the sludge-based catalyst prepared under the conditions of example 8 are preferable, but the increase of the mixing liquid stirring time and drying temperature of comparative example 1 and example 8 has less influence on the specific surface area and total pore volume of the sludge-based catalyst; therefore, embodiment 1 is more preferable.
4. Researching 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 experimental comparisons of example 1, example 9, and example 10 are shown in table 4 below:
TABLE 4 specific surface area and pore distribution of the sludge-based catalyst under different parameters of the first activation protocol
Parameter(s) 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 prepared catalyst are correspondingly increased by increasing the activation temperature and increasing the activation time, but the variation range of the specific surface area of example 10 is not obvious compared with that of example 1, but the higher activation temperature and activation time are adopted, and example 1 is preferred from the viewpoint of production cost and the like.
5. The influence of the component proportion of the added first-stage activating agent and the second-stage activating agent on the specific surface area and pore distribution of the prepared sludge-based catalyst is explored in another activation scheme;
taking the first-stage activator and the second-stage activator in the embodiment 11 as references, 2-hydroxyethylamine is not added into the first-stage activator and the second-stage activator, and the rest components are kept unchanged and are recorded as a comparative example 2;
the results of experimental comparisons of control 2, example 1, example 11, example 12 and example 13 are shown in table 5 below:
TABLE 5 component proportions of the first and second activators of another activation protocol the specific surface area and pore distribution of the sludge-based catalyst
Parameter(s) 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 schemes of example 1 and example 11 are better than those of example 11 with the addition of the activator;
through comparative example 11, example 12 and example 13, when the component distribution ratio in the primary activator and the component distribution ratio in the secondary activator are changed, the comparative surface area, the total pore volume and the average pore diameter are all influenced, and example 11 is preferable; meanwhile, through the comparative example 11 and the comparative example 2, when the 2-hydroxyethylamine is not added into the first-stage activator and the second-stage activator, the specific surface area of the prepared sludge-based catalyst is obviously reduced; in view of the above, embodiment 11 is preferable.
6. Researching 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 experimental comparisons of example 11, example 14, and example 15 are shown in table 6 below:
TABLE 6 specific surface area and pore distribution of sludge-based catalysts under different parameters of another activation protocol
Parameter(s) 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, by comparing examples 11, 14 and 15, the stirring time of the first-order activator was increased, and CO in the activated gas was increased 2 The specific surface area and pore distribution of the sludge-based catalyst are increased, along with CO 2 The content of (a) is continuously increased, but the total pore volume of the sludge-based catalyst is still increased but is gradually not obvious, but the specific surface area is reduced, so that the parameters of the example 11 are better in combination.
7. The influence of a spraying mode of adding a secondary activating agent in another activation 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 activating agent on the surface of the dried solid at a spraying speed of 0.2ml/min, carrying out 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 deg.C to 450 deg.C at a heating rate of 8 deg.C/min, adjusting the spraying speed of 0.18ml/min for each 8 deg.C increase, spraying onto the surface of the dried solid, activating the dried solid for the second time, stopping heating at 450 deg.C, and cooling to room temperature.
Comparative examples 3, 4, 11, 18 and 19 were used as experimental comparisons and the results are shown in table 7 below:
TABLE 7 specific surface area and pore distribution of sludge-based catalysts in secondary activator spray mode of another activation protocol
Parameter(s) 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, when comparative examples 3 and 4 are compared with example 11, the spraying speed is constant in comparative example 3, and the spraying speed is continuously increased in comparative example 4, but the specific surface area of the sludge-based catalyst prepared in comparative examples 3 and 4 is obviously reduced, and example 11 is preferable;
by comparing examples 18 and 19 with example 11, the specific surface area of the prepared sludge-based catalyst is influenced by different temperature nodes of the switching of the spraying speed, wherein example 11 is preferred.
8. The spraying speed of a secondary activating agent added in another activation scheme and the influence of the spraying speed change on the specific surface area and pore distribution of the prepared sludge-based catalyst are researched;
the results of experimental comparisons of example 11, example 16, example 17, example 20, example 21, example 22 and example 23 are shown in table 8 below:
TABLE 8 Secondary activators for alternative activation schemes different spray rates and specific surface area and pore distribution of sludge-based catalysts with different spray rate variations
Parameter(s) 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 spray rate has an effect on the surface area, total pore volume and average pore size, and from a general standpoint, example 11 is preferred;
by comparing example 11, example 20, example 21, example 22 and example 23, the different increasing/decreasing rates of the spraying speed have some influence on the specific surface area of the prepared sludge-based catalyst, of which example 11 is preferred;
the effect of different initial spraying speeds on the sludge-based catalyst is evident by comparing example 11, example 16 and example 17, of which example 11 is preferred.
Experiment two: in order to further compare the above examples, the prepared oxalic acid solution and a sample of petrochemical wastewater collected from a certain petrochemical sewage plant in Jilin city were treated with the sludge-based catalysts prepared in examples 1, 11 and 1 to 4, respectively, and the following were studied:
1. carrying out an oxalic acid wastewater experiment by using the prepared sludge-based catalyst;
(1) Evaluating the adsorption efficiency of the sludge-based catalyst by utilizing a sludge-based catalyst adsorption oxalic acid experiment;
1g/L of different types of sludge-based catalysts are added into oxalic acid with the initial concentration of 100mg/L for carrying out an adsorption treatment experiment, oxygen with the flow rate of 300mL/min is introduced, stirring is carried out at room temperature, and the oxalic acid removal rate and the TOC removal rate are shown in a table 9 at 60 min:
TABLE 9 oxalic acid removal rate TOC removal rate by adsorption of sludge-based catalyst on oxalic acid experiment
Group of Removal rate of oxalic acid 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 has the best effect on the adsorption removal of oxalic acid, and the adsorption efficiency is the highest; and comparative example 1, in which no Mn salt was added, had the lowest oxalic acid removal rate and TOC removal rate;
(2) Evaluating the catalytic effect of the sludge-based catalyst by utilizing a sludge-based catalyst catalytic ozone treatment oxalic acid experiment;
comparative example 5: only 300mL/min and 33mg/L ozone is introduced into oxalic acid with the initial concentration of 100mg/L without adding a sludge-based catalyst, and the mixture is stirred at room temperature;
experimental example: 1g/L of different types of sludge-based catalysts are added into oxalic acid with the initial concentration of 100mg/L to carry out catalytic ozone oxidation treatment experiments, ozone with the flow rate of 300mL/min and the concentration of 33mg/L is led in, 100mg/L of tertiary butanol and p-benzoquinone with all concentrations are added, stirring is carried out at room temperature,
oxalic acid removal and TOC removal at 20min are shown in table 10:
TABLE 10 TOC removal rate of oxalic acid removal rate 20min in sludge-based catalyst catalyzed oxalic acid experiment
Group of Removal rate of oxalic acid 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 TOC removal rate of 60min oxalic acid removal rate of sludge-based catalyst catalyzed oxalic acid experiment
Group of Removal rate of oxalic acid 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 of example 11 is nearly completely removed at 20min, and the removal rate of the oxalic acid in the system for catalyzing ozonization degradation of the oxalic acid by the sludge-based catalyst prepared by each group of examples is gradually increased at 60min along with the increase of the pyrolysis temperature; example 11 was selected as the optimum in view of the economy of preparing the sludge-based catalyst;
furthermore, it can be seen that the sludge-based catalyst prepared in example 11 has much higher ability to catalyze ozone treatment of oxalic acid and TOC than comparative example 1 and comparative example 5.
2. Carrying out a petrochemical wastewater experiment by using the prepared sludge-based catalyst;
evaluating the adsorption efficiency and the catalysis efficiency of the sludge-based catalyst by utilizing an experiment of catalyzing ozone to treat petrochemical wastewater by using the sludge-based catalyst;
experimental example: respectively adding 1g of the sludge-based catalysts of the embodiment 1 and the embodiment 11 into 1L of petrochemical wastewater, introducing 24mg/L of ozone at 300mL/min, adding 100mg/L of tert-butyl alcohol and p-benzoquinone at the same concentration, and stirring at room temperature; obtaining petrochemical wastewater after catalytic purification;
comparative example 6: adding 1g of the sludge-based catalyst obtained in example 1 into 1L of petrochemical wastewater, introducing oxygen at 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 to 1L of petrochemical wastewater, introducing oxygen at 300mL/min, and stirring at room temperature; obtaining petrochemical wastewater after catalytic purification;
comparative example 8: only 300mL/min and 24mg/L ozone is introduced into 1L of petrochemical wastewater without adding a sludge-based catalyst; stirring at room temperature; obtaining petrochemical wastewater after catalytic purification;
TOC removal Rate UV at 30min 254 The removal rates are shown in Table 12:
TABLE 12 sludge-based catalyst catalysis/adsorption petrochemical wastewater experiment 30minTOC removal rate UV 254 Removal rate of
Group of TOC removal Rate UV 254 Removal rate
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, the catalytic ozone treatment efficiency was found in comparative examples 1, 6 and 8 after the reaction proceeded for 30min>Efficiency of adsorption treatment>The efficiency of ozone treatment alone will be described with respect to comparative example 6, example 1 and example 11, with respect to TOC removal rate and UV after addition of sludge-based catalyst 254 The removal rates were all increased, with example 11 being optimal;
meanwhile, the removal effect was improved in comparative examples 2, 3 and 4 as compared with example 1.

Claims (9)

1. A method for preparing a sludge-based catalyst by utilizing petrochemical excess sludge 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 the sludge powder, the Mn salt and the agar powder into ultrapure water according to a proportion, stirring for 0.5 to 2h, then adding ammonia water, and continuously stirring for 2 to 4h to obtain a mixed solution;
s3, drying and pyrolyzing:
activating and drying the mixed solution to obtain a solid, putting the solid into a tubular furnace, heating to 500-800 ℃, keeping the temperature for 0.5-1.5 h, and cooling the solid to room temperature in the tubular furnace;
s4, cooling and cleaning:
and taking out the solid from the tubular furnace, washing the solid for multiple times by using ethanol and ultrapure water, drying and crushing the solid, and sieving the solid to obtain the sludge-based catalyst.
2. The method for preparing the sludge-based catalyst from the petrochemical excess sludge according to claim 1, wherein the drying temperature in the steps S1 and S4 is 100 to 120 ℃, and the mesh size of the mesh sieved in the steps S1 and S4 is 100 meshes.
3. The method for preparing a sludge-based catalyst using petrochemical excess sludge according to claim 1, wherein the Mn salt in the step S2 is MnCl 2 The sludge powder, mnCl 2 And the mass ratio of the agar powder to the agar powder is 0.9 to 1.5, and 0.8 to 1.2; the proportion of sludge powder, ultrapure water and ammonia water is 1g.
4. The method for preparing a sludge-based catalyst using petrochemical excess sludge according to claim 1, wherein the activating method in the step S3 is: and (3) treating the mixed solution in an oven at a constant temperature of 110-280 ℃ for 2-3 h to obtain an activated solid.
5. The method for preparing the sludge-based catalyst using the petrochemical surplus sludge according to claim 1, wherein the inert gas is any one of helium, argon and neon in the step S3, and the heating rate is 10 ℃/min.
6. The method for preparing a sludge-based catalyst using petrochemical excess sludge according to claim 1, wherein the activation method in the step S3 is:
s3-1, adding a primary activating agent into the mixed solution, and continuously stirring for 6 to 8h for primary activation; then dehydrating and drying the mixed solution obtained after the primary activation to obtain a dry solid;
s3-2, putting the dry solid into a tubular furnace, heating the dry solid from 25 ℃ at a heating rate of 8 ℃/min under an activated gas atmosphere with constant concentration, uniformly spraying a secondary activating agent on the surface of the dry solid at an initial spraying speed of 0.15 to 0.2ml/min, wherein the spraying speed of the secondary activating agent is adjusted along with the temperature of the dry solid;
the spraying speed of the secondary activator is adjusted along with the temperature of the dry solid by the following method: before the temperature reaches 300 to 330 ℃, the spraying speed of the secondary activator is increased by 0.01 to 0.015ml/min along with the temperature rise of 8 ℃; after the temperature reaches 300 to 330 ℃, the spraying speed of the secondary activator is reduced by 0.02 to 0.03ml/min along with the temperature rise of 8 ℃; and stopping heating until the spraying speed of the secondary activating agent is zero, and then cooling to room temperature.
7. The method according to claim 6, wherein the activated gas atmosphere contains CO in a concentration of 1.5 to 4.5% by volume 2 And the balance being inert gas and/or nitrogen.
8. The method of claim 6, wherein the primary activator in step S3 is 2-hydroxy groupEthylamine, KOH, znCl 2 And (2) the ratio of (1) to (2) is 0.5 to 0.8:1:0.5 to 0.8 in mass ratio; the secondary activating agent is 2-hydroxyethylamine, KOH, znCl 2 And ultrapure water in a ratio of 1:0.5 to 0.8:0.2 to 0.5:10 by mass ratio.
9. The application of the sludge-based catalyst prepared by the method for preparing the sludge-based catalyst from the petrochemical excess sludge according to any one of claims 1 to 8 is characterized in that 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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