CN115672283A - Preparation method and application of degraded fuel-resistant chitosan/bentonite composite adsorbent - Google Patents

Preparation method and application of degraded fuel-resistant chitosan/bentonite composite adsorbent Download PDF

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CN115672283A
CN115672283A CN202211365332.0A CN202211365332A CN115672283A CN 115672283 A CN115672283 A CN 115672283A CN 202211365332 A CN202211365332 A CN 202211365332A CN 115672283 A CN115672283 A CN 115672283A
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chitosan
bentonite
oil
resistant
composite adsorbent
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蔡萱
蔡世腾
任贝婷
蒋晶晶
李钟灵
安乐天
任乔林
郑辉
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State Grid Corp of China SGCC
Electric Power Research Institute of State Grid Hubei Electric Power Co Ltd
Xiaogan Power Supply Co of State Grid Hubei Electric Power Co Ltd
Suizhou Power Supply Co of State Grid Hubei Electric Power Co Ltd
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State Grid Corp of China SGCC
Electric Power Research Institute of State Grid Hubei Electric Power Co Ltd
Xiaogan Power Supply Co of State Grid Hubei Electric Power Co Ltd
Suizhou Power Supply Co of State Grid Hubei Electric Power Co Ltd
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Abstract

The invention provides a preparation method and application of a degraded fuel-resistant chitosan/bentonite composite adsorbent. The degraded fuel-resistant chitosan/bentonite composite adsorbent is obtained by dispersing chitosan into hydrochloric acid aqueous solution with the concentration of 4%, then adding bentonite, continuously stirring for 2.5-3.5 h at the temperature of 90-98 ℃ and the rotating speed of 700-900 rpm, mixing, centrifuging, collecting solid substances, drying in an oven, and calcining for 1-2 h at the temperature of 250-350 ℃ in the argon atmosphere. The chitosan/bentonite composite adsorbent is used for deacidifying and decoloring the degraded fire-resistant oil, the acid content of the treated fire-resistant oil is greatly reduced, the color of the treated fire-resistant oil is as bright as that of a new fire-resistant oil, and the requirements of the operation and maintenance guide rules of the phosphate fire-resistant oil for DL-T571-2007 power plants can be met.

Description

Preparation method and application of degraded fuel-resistant chitosan/bentonite composite adsorbent
Technical Field
The invention belongs to the field of energy conservation and environmental protection, and particularly relates to a preparation method of a chitosan/bentonite composite adsorbent and application of the chitosan/bentonite composite adsorbent in adsorption of degraded fire-resistant oil.
Background
The fire-resistant oil is mainly used for a turbine speed regulating system of a power system generator set, has the effects of speed regulation, lubrication and cooling, has the impurity degree, moisture and acidity as the most main factors influencing the quality of the fire-resistant oil, is influenced by the three factors, increases the acid value of the fire-resistant oil when the fire-resistant oil is degraded and hydrolyzed, and causes the corrosion of various elements of equipment due to the corrosion of acid, generates particle impurities, bubbles and the like.
The fit clearance of parts such as an electromagnetic valve, a servo valve and the like in the turbine electro-hydraulic regulating system is small, and particularly the clearance between a nozzle and a baffle of the servo valve and the clearance between a valve core and a valve sleeve are small. When elements in the components such as the electromagnetic valve, the servo valve and the like are corroded, the fit clearance is increased, the oil leakage amount of the clearance of each component is increased, and the flow of the EH system is increased from the surface. Due to the increase of the flow, the scouring of fuel pipelines, pipeline elbows, electromagnetic valves, servo valves and the like is aggravated, so that the pipe wall becomes thinner, the fit clearance of each part becomes larger, and the damage is caused. The gas bubbles produced by corrosion are separated during operation, in particular during throttling, in the region of a small local pressure reduction, and the gas is released from the oil at an accelerated rate. The work of the EH system is unstable, so that parts such as pipelines, servo valves, electromagnetic valves, unloading valves and the like are vibrated, the operation of the EH oil pump is influenced, and the aging of the fire-resistant oil is accelerated. Impurities such as tiny particles generated by corrosion easily cause jamming of components such as an electromagnetic valve and a servo valve, the service life of each component is influenced, an EH system cannot be adjusted normally, and safe operation of a unit is endangered. The development of the fire-resistant oil adsorption tank has important practical significance for enterprises to carry out clean production, save resources and develop circular economy.
Disclosure of Invention
The invention provides a preparation method and application of a degraded fuel-resistant chitosan adsorbent according to the defects of the prior art, the adsorbent prepared by the method can well perform deacidification and decoloration treatment on degraded fuel-resistant oil, and the treated fuel-resistant oil can reach the standard of new fuel-resistant oil and can be recycled.
In order to achieve the aim, the invention provides a preparation method of a degraded fuel-resistant chitosan/bentonite composite adsorbent, which is characterized by comprising the following specific steps:
(1) Dispersing chitosan into hydrochloric acid aqueous solution with the concentration of 4 percent, then adding bentonite, continuously stirring for 2.5-3.5 h at the temperature of 90-98 ℃ and the rotating speed of 700-900 rpm, and uniformly mixing; wherein, the mass fraction of the chitosan in the bentonite is 4.5-5.5%; the mass volume ratio of the bentonite to the hydrochloric acid aqueous solution with the concentration of 4 percent is 2.5-3.5g;
(2) Centrifuging the mixed solution in the step (1), collecting solid substances, and placing the solid substances in an oven at 105-110 ℃ for 4.5-5.5 hours until the solid substances are dried;
(3) And (3) calcining the dried substance in the step (2) for 1-2 h in an argon atmosphere at 250-350 ℃ to obtain the chitosan/bentonite composite adsorbent.
The invention has the following excellent technical scheme: the addition amount of the chitosan in the step (1) is 5% of the mass of the bentonite; the calcination temperature in the step (3) is 300 ℃.
In order to achieve the technical purpose, the invention also provides application of the degraded fuel-resistant chitosan/bentonite composite adsorbent, and specifically the chitosan/bentonite composite adsorbent prepared by the method is used for deacidifying the degraded fuel-resistant oil.
The further technical scheme of the invention is as follows: filling the chitosan/bentonite composite adsorbent into a degraded fire-resistant oil adsorption tank to replace an activated carbon adsorbent or a chitosan adsorbent, and controlling the space velocity of the adsorption tank to be 12-49 h -1 Then the adsorption tank is connected with an EH oil filter to filter the degraded fire-resistant oil, the filtering temperature is controlled between 55 ℃ and 65 ℃, and the filtering treatment lasts for 23 hours to 25 hours.
The further technical scheme of the invention is as follows: the deterioration fire-resistant oil adsorption tank comprises a tank body and a sealing cover, wherein a sealing gasket of the sealing cover is a circular fluororubber sealing gasket; an oil inlet is formed in the sealing cover, an oil outlet is formed in the side face of the tank body, a back flushing port is formed in the bottom of the tank body, a filter element filled with chitosan/bentonite composite adsorbent is arranged in the tank body, the filter element comprises a cylindrical filter screen and a filter bag filled with the chitosan/bentonite composite adsorbent, the height of the cylindrical filter screen is equal to that of the tank body, and the diameter of the cylindrical filter screen is smaller than the inner diameter of the tank body; the oil inlet leads to the filter element, and the oil outlet leads to the space between the filter element and the tank body.
According to the invention, the adsorbent adopts inorganic bentonite for chitosan modification, chitosan is intercalated into the inorganic bentonite, the pore diameter of the inorganic bentonite can be enlarged due to the residual chitosan carbon structure after roasting, the enlarged pores can just enable the fire-resistant oil to be drilled into the bentonite due to the large molecular weight of the fire-resistant oil, and the roasted chitosan can generate more amino groups, so that the deacidification treatment can be well carried out on the fire-resistant oil drilled into the bentonite; and the bentonite has strong decolorizing capability and the deacidification effect of the amino group can well adsorb colored acid in the inferior fire-resistant oil, so that the acid content of the treated fire-resistant oil is greatly reduced, the color of the treated fire-resistant oil is as bright as that of a new fire-resistant oil, and the requirements of the operation and maintenance guide rules of the phosphate fire-resistant oil for DL-T571-2007 power plants can be met.
Drawings
FIG. 1 is a schematic view of the construction of an adsorption tank in the present invention;
FIG. 2 is a schematic diagram of a canister cartridge according to the present invention;
3-A and 3-C are TEM images of the BT adsorbent material of the first example;
3-B and 3-D are TEM images of the C5/BT-300 composite adsorbent prepared in example one;
FIG. 4 is a table comparing the decolorization of fuel resistant oils by different adsorbents in test two;
figure 5 is a graph of the comparative results of the fire-resistant oil treated with different adsorbents in comparative experiment two.
In the figure: 1-tank body, 2-sealing cover, 3-oil inlet, 4-oil outlet, 5-filter core, 500-cylindrical filter screen, 501-filter bag, 502-chitosan/bentonite composite adsorbent and 6-back flushing port.
Detailed Description
The invention is further illustrated by the following examples in conjunction with the drawings. The following claims presented in the drawings are specific to embodiments of the invention and are not intended to limit the scope of the claimed invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The deterioration-resistant fuel adsorption tank used in the embodiment of the invention, as shown in fig. 1 and fig. 2, comprises a tank body 1 and a sealing cover 2, wherein the sealing gasket of the sealing cover 2 is a circular fluorine rubber sealing gasket; an oil inlet 3 is formed in the sealing cover 2, an oil outlet 4 is formed in the side face of the tank body 1, a back flushing port 6 is formed in the bottom of the tank body 1, a filter element 5 filled with a chitosan/bentonite composite adsorbent is arranged in the tank body 1, the filter element comprises a cylindrical filter screen 500 and a filter bag 501 filled with a chitosan/bentonite composite adsorbent 502, the height of the cylindrical filter screen 500 is equal to that of the tank body, and the diameter of the cylindrical filter screen is smaller than the inner diameter of the tank body 1; the oil inlet 3 leads to the filter element 5, and the oil outlet 3 leads to the space between the filter element 5 and the tank body 1.
The embodiment provides a preparation method of a degraded fuel-resistant chitosan/bentonite composite adsorbent, which comprises the following specific preparation steps:
(1) Dispersing Chitosan (CS) accounting for 5% of the mass fraction of Bentonite (BT) into 200ml of hydrochloric acid aqueous solution with the volume fraction of 4%, then adding 30g of bentonite, continuously stirring for 3h at the temperature of 95 ℃ and the rotating speed of 800rpm, and uniformly mixing;
(2) Centrifuging the mixed solution in the step (1), collecting solid substances, and placing the solid substances in an oven at 105 ℃ for 5 hours until the solid substances are dried;
(3) Calcining the dried substance in the step (2) for 1h in an argon atmosphere at 300 ℃ to obtain the chitosan/bentonite composite adsorbent, which is named as: C5/BT-300 composite material adsorbent.
The C5/BT-300 composite adsorbent prepared in the first example and Bentonite (BT) are respectively observed by a Transmission Electron Microscope (TEM), and the observation result is shown in figure 3; as can be seen in fig. 3-a and 3-C, the BT adsorbent material has a compact, uniform internal structure without significant wrinkling features or coverings; the C5/BT-300 composite prepared when BT was modified with CS and calcined at 300 ℃ as shown in figures 3-C and 3-D clearly showed non-uniform morphology, while some non-uniform matter was seen covering the surface of BT, which was mainly carbon formed by CS carbonization. In appearance, BT is in a light red powder structure, and C5/BT-300 is in a gray black powder structure, which more visually indicates that CS is carbonized to form carbon, thereby further indicating that CS is used for successfully modifying BT.
Example two: the C5/BT-300 composite material adsorbent prepared in the first embodiment is applied to a simulation test treatment of waste degraded fire-resistant oil of an east lake gas turbine power plant, wherein a 0.5 kilogram degraded fire-resistant oil adsorption tank is adopted in the specific treatment process,the volume of the adsorbent is 1.22 liters, the flow rate is 1 liter/min, and the space velocity is 49h -1 (ii) a Opening the upper cover, loading the adsorption filter element filled with the C5/BT-300 composite material adsorbent into an adsorption tank, covering the upper cover, namely loading the adsorption tank, then connecting the adsorption tank into the existing EH oil filter, filtering at 50 ℃, and performing deacidification and decoloration treatment after filtering and adsorption for 10 hours, wherein the treatment results are shown in Table 1:
TABLE 1 oil simulation test of east lake gas turbine power plant C5/BT-300 adsorption effect
Figure BDA0003916490720000051
As can be seen from the table 1, the acid value of the adsorbed fire-resistant oil is greatly reduced, and the foam characteristics of the adsorbed fire-resistant oil also meet the use standard of the fire-resistant oil; the treated fire-resistant oil can be reused.
Example three: the C5/BT-300 composite adsorbent prepared in the first embodiment is applied to an east lake gas turbine power plant for on-site treatment of waste degraded fire-resistant oil of the power plant, and a 20 kg degraded fire-resistant oil adsorption tank is adopted, wherein the adsorption tank has the diameter of 400mm and the height of a pile layer of 40mm, and the specific gravity of the adsorbent is 0.41kg/L. The flow rate is 10L/min, and the space velocity is about 12h -1 Treating 0.5 tons of waste EH oil; the process was the same as in the example, and the results are shown in Table 2:
TABLE 2 oil in-situ test C5/BT-300 adsorption effect of combustion engine power plant in east lake
Figure BDA0003916490720000061
As can be seen from Table 2, the acid value of the adsorbed fire-resistant oil is greatly reduced, and the foam characteristics after adsorption also meet the use standard of the fire-resistant oil; the foam property of the treated EH oil is reduced and qualified after treatment, and the EH oil can be reused.
Example four: the C5/BT-300 composite material adsorbent prepared in the first example is applied to the unit of the applicationTreating the degraded fire-resistant oil, wherein 5 kg of waste filter element and 250 g of adsorbent are adsorbed for 8 hours, the flow rate is 160 liters/hour, and the space velocity is 12.8 hours -1 The acid value of the deteriorated fuel oil before adsorption was 0.16mg KOH/g, and the acid value after adsorption was 0.07mg KOH/g.
Comparison test one: respectively dispersing Chitosan (CS) accounting for 1%, 3%, 5%, 7% and 9% of the mass fraction of Bentonite (BT) in 200ml of hydrochloric acid aqueous solution with the volume fraction of 4%, then adding 30g of BT, and continuously stirring for 3h at the temperature of 95 ℃ and the rotating speed of 800 rpm; then, respectively centrifuging the mixed solution, and placing the obtained solid substances in a drying oven at 105 ℃ for about 5 hours until the solid substances are dried; calcining the dried substances at 200 ℃, 250 ℃, 300 ℃, 350 ℃ and 400 ℃ respectively in an argon atmosphere for 1h to prepare chitosan/bentonite composite adsorbents with different models, wherein the specific models are shown in Table 3;
TABLE 3 preparation of chitosan/bentonite composite adsorbents of different types
Figure BDA0003916490720000071
Then, the chitosan/bentonite composite adsorbents with different types, pure BT and CS are respectively added into an adsorption tank to treat degraded oil, the best preparation conditions of the chitosan/bentonite composite adsorbents are screened through tests, the influence of the composite adsorbents prepared by the addition of chitosan and the calcination temperature on the decoloration of the waste transformer oil is inspected, and the test results are shown in table 4:
TABLE 4 variation of the electrical properties of the oil sample before and after adsorption of the degraded fire-resistant oil by different types of adsorbents
Figure BDA0003916490720000072
Figure BDA0003916490720000081
As can be seen from Table 4, the optimal addition amount of chitosan is 5% and the roasting temperature is 300 ℃, the degraded oil breakdown voltage capability of the chitosan/bentonite composite adsorbent C5/BT-300 prepared under the condition is optimal, the dielectric loss factor is lowest, the moisture is least, and the acid value is also lowest; and C5/BT-300 is adsorbed and added into an adsorption tank, and is treated with other existing filtering equipment, and the characteristic pairs of the degraded oil before and after treatment are as follows:
Figure BDA0003916490720000082
comparative experiment two: comparing the decolorizing conditions of the fire resistant oil of different adsorbents; in the experiment, the most commonly used Bentonite (BT), granular activated Carbon adsorbent (Carbon) and C5/BT-300 composite material are selected for comparison of the decolorization effect; as a result of comparison, as shown in FIGS. 4 and 5, it was found that the light transmittance of the transformer oil (unordered) before the decoloring treatment was 70.1%, and the color number was 10; after the granular activated Carbon (Carbon) adsorbs oil, the light transmittance of the oil is 74%, and the color number is 9, which indicates that the pure granular activated Carbon has poor decolorizing effect on the transformer oil. When pure BT is used as an adsorbent, the light transmittance of the transformer oil is remarkably improved, the color number is also reduced from No. 10 to No. 6, but the appearance of the oil still presents faint yellow. The light transmittance of the oil product adsorbed by the C5/BT-300 composite material can reach 99.5 percent, the color number is reduced to No. 1, and the appearance of the oil product is almost similar to that of colorless transparent new oil. In conclusion, the decolorizing performance of the C5/BT-300 composite material is superior to that of other adsorbents.
The foregoing is only a few embodiments of the present invention, and the description is specific and detailed, but not intended to limit the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present invention should be subject to the appended claims.

Claims (5)

1. A preparation method of a degraded fuel-resistant chitosan/bentonite composite adsorbent is characterized by comprising the following specific steps:
(1) Dispersing chitosan into hydrochloric acid aqueous solution with the concentration of 4 percent, then adding bentonite, continuously stirring for 2.5-3.5 h at the temperature of 90-98 ℃ and the rotating speed of 700-900 rpm, and uniformly mixing; wherein, the mass fraction of the chitosan in the bentonite is 4.5-5.5%; the mass volume ratio of the bentonite to the hydrochloric acid aqueous solution with the concentration of 4 percent is 2.5-3.5g;
(2) Centrifuging the mixed solution in the step (1), collecting solid substances, and placing the solid substances in a drying oven at 105-110 ℃ for 4.5-5.5 h until the solid substances are dried;
(3) And (3) calcining the dried substance in the step (2) for 1-2 h in an argon atmosphere at 250-350 ℃ to obtain the chitosan/bentonite composite adsorbent.
2. The method for preparing the degraded fuel-resistant chitosan/bentonite composite adsorbent according to claim 1, wherein: the addition amount of the chitosan in the step (1) is 5% of the mass of the bentonite; the calcination temperature in the step (3) is 300 ℃.
3. The application of the degraded fuel-resistant chitosan/bentonite composite adsorbent is characterized in that: the chitosan/bentonite composite adsorbent prepared by the method of any one of claims 1 or 2 is used for deacidifying and decolorizing the degraded fire-resistant oil.
4. The use of a chitosan/bentonite composite adsorbent for degrading fuel oil resistance according to claim 3, wherein: filling the chitosan/bentonite composite adsorbent into a degraded fire-resistant oil adsorption tank to replace an activated carbon adsorbent or a chitosan adsorbent, and controlling the space velocity of the adsorption tank to be 12-49 h -1 Then the adsorption tank is connected with an EH oil filter to filter the degraded fire-resistant oil, the filtering temperature is controlled between 55 ℃ and 65 ℃, and the filtering treatment lasts for 23 hours to 25 hours.
5. The use of the chitosan/bentonite composite adsorbent for degrading fuel oil resistance according to claim 4, wherein: the deterioration fire-resistant oil adsorption tank comprises a tank body (1) and a sealing cover (2), wherein a sealing gasket of the sealing cover (2) is a round fluororubber sealing gasket; an oil inlet (3) is formed in the sealing cover (2), an oil outlet (4) is formed in the side face of the tank body (1), a back flushing port (6) is formed in the bottom of the tank body (1), a filter core (5) filled with a chitosan/bentonite composite adsorbent is arranged in the tank body (1), the filter core comprises a cylindrical filter screen (500) and a filter bag (501) filled with a chitosan/bentonite composite adsorbent (502), the height of the cylindrical filter screen (500) is equal to that of the tank body, and the diameter of the cylindrical filter screen is smaller than the inner diameter of the tank body (1); the oil inlet (3) leads to the filter element (5), and the oil outlet (3) leads to the space between the filter element (5) and the tank body (1).
CN202211365332.0A 2022-10-31 2022-10-31 Preparation method and application of degraded fuel-resistant chitosan/bentonite composite adsorbent Pending CN115672283A (en)

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Citations (3)

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CN208541891U (en) * 2018-06-28 2019-02-26 国网湖北省电力有限公司孝感供电公司 A kind of oil-filtering apparatus handling waste transformer oil
CN112337443A (en) * 2020-11-04 2021-02-09 国网湖北省电力有限公司孝感供电公司 Mixed adsorbent for deteriorated transformer insulating oil and using method and device thereof

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Publication number Priority date Publication date Assignee Title
CN208422606U (en) * 2018-06-28 2019-01-22 国网湖北省电力有限公司孝感供电公司 A kind of filter-press handling waste transformer oil
CN208541891U (en) * 2018-06-28 2019-02-26 国网湖北省电力有限公司孝感供电公司 A kind of oil-filtering apparatus handling waste transformer oil
CN112337443A (en) * 2020-11-04 2021-02-09 国网湖北省电力有限公司孝感供电公司 Mixed adsorbent for deteriorated transformer insulating oil and using method and device thereof

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