CN115228455A - Catalyst for treating waste oil, preparation method and application thereof, and waste oil treatment method - Google Patents
Catalyst for treating waste oil, preparation method and application thereof, and waste oil treatment method Download PDFInfo
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- CN115228455A CN115228455A CN202110433164.3A CN202110433164A CN115228455A CN 115228455 A CN115228455 A CN 115228455A CN 202110433164 A CN202110433164 A CN 202110433164A CN 115228455 A CN115228455 A CN 115228455A
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- 239000002699 waste material Substances 0.000 title claims abstract description 84
- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003921 oil Substances 0.000 claims abstract description 98
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 73
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 72
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 31
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 230000003197 catalytic effect Effects 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 238000001035 drying Methods 0.000 claims description 26
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 18
- 239000010913 used oil Substances 0.000 claims description 18
- 239000004094 surface-active agent Substances 0.000 claims description 15
- 239000002270 dispersing agent Substances 0.000 claims description 14
- 230000009467 reduction Effects 0.000 claims description 14
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 14
- 239000012279 sodium borohydride Substances 0.000 claims description 14
- 230000004048 modification Effects 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 238000010306 acid treatment Methods 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 9
- -1 polyoxyethylene Polymers 0.000 claims description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- 238000001879 gelation Methods 0.000 claims description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 150000003973 alkyl amines Chemical class 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000008569 process Effects 0.000 abstract description 20
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 17
- 239000000377 silicon dioxide Substances 0.000 abstract description 16
- 239000000084 colloidal system Substances 0.000 abstract description 12
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 9
- 239000012535 impurity Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 125000000524 functional group Chemical group 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000006482 condensation reaction Methods 0.000 abstract description 2
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 15
- 238000005491 wire drawing Methods 0.000 description 14
- 238000001914 filtration Methods 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 239000011734 sodium Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 229920000151 polyglycol Polymers 0.000 description 6
- 239000010695 polyglycol Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000010730 cutting oil Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000010720 hydraulic oil Substances 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1003—Waste materials
- C10G2300/1007—Used oils
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention provides a catalyst for treating waste oil, a preparation method and application thereof, and a waste oil treatment method, and belongs to the technical field of waste oil treatment. According to the method, water glass is used as a raw material, acetic acid and the water glass are reacted to generate silicic acid colloid, the silicic acid colloid is dried to obtain silicon dioxide powder, the silicon dioxide powder is modified to obtain silicon dioxide containing-OH or-O, functional groups of the catalyst are increased, the adsorption effect of the catalyst on impurities in the waste oil is favorably improved, and the catalytic treatment of the waste oil is realized through the condensation reaction of the increased functional groups and the impurities in the waste oil. The method has the advantages of abundant materials, low cost, energy conservation, environmental protection, simple process and high efficiency. The prepared catalyst is used for treating waste oil, the waste oil treatment effect is excellent, the repeatability is good, the catalyst can be recycled, the cost can be reduced, the resource utilization rate is increased, and the economic benefit is increased.
Description
Technical Field
The invention relates to the technical field of waste oil treatment, in particular to a catalyst for treating waste oil, a preparation method and application thereof, and a waste oil treatment method.
Background
With the development of the times, people now use more and more industrial oil, so that a lot of waste oil is generated, such as: hydraulic oil, wire drawing oil, white oil, lubricating oil, cutting oil and the like, waste oil is directly discharged into the environment, and the environment is polluted because harmful substances contained in the waste oil are difficult to degrade. At present, the treatment method of waste oil mainly comprises the following steps: 1. the waste oil is directly converted into low-end fuel for combustion, but secondary pollution to the environment is caused, the resource utilization rate is low, and meanwhile, resource waste is caused; 2. the waste oil is treated by the oil refining process, but the method has the disadvantages of complex process, more equipment and large investment, and is difficult to be suitable for industrialization. Therefore, neither of the above-mentioned methods is suitable for waste oil treatment.
Currently, green chemistry, environmentally friendly processes are becoming more and more favored by the chemical industry, and the use of catalysts is one of the main methods for implementing green chemistry. At present, chemical articles are treated by catalysts to have the effect of reducing environmental pollution, and the catalysis has a vital effect on the chemical industry. Therefore, it is important to prepare a catalyst for treating waste oil by a simple method so as to achieve the purpose of waste oil treatment.
Disclosure of Invention
The invention aims to provide a catalyst for treating waste oil, a preparation method and application thereof, and a waste oil treatment method.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a catalyst for treating waste oil, which comprises the following steps:
mixing water glass, a surfactant, acetic acid and water, and gelatinizing to obtain gel;
mixing the gel, the dispersing agent and water, and sequentially dispersing and drying the obtained mixture to obtain silicon dioxide powder;
modifying the silicon dioxide powder to obtain a catalyst for treating waste oil;
the modification treatment method comprises acid treatment, alkali treatment-sodium borohydride reduction treatment or hydrogen peroxide treatment.
Preferably, the surfactant comprises long-chain fatty alcohol-polyoxyethylene ether, alkylphenol ethoxylate, fatty acid polyoxyethylene ester, polyoxyethylene alkylamine, polyoxyethylene alkylamide or polyether.
Preferably, the molar ratio of the water glass to the surfactant is (400-2000): 1; the molar ratio of the acetic acid to the water glass is (1-2) to 1.
Preferably, the temperature of the gelation is 20 to 110 ℃ and the time is 16 to 24 hours.
Preferably, the dosage ratio of the gel to the water is (1-10) g:100mL.
Preferably, the dispersant is polyvinylpyrrolidone, polyether derivatives or polyethylene glycol; the concentration of the dispersant in the mixture is 2-10 mmol/L.
Preferably, the dispersion is carried out under stirring conditions; the dispersing time is 4h; the drying temperature is 50-130 ℃, and the drying time is 6-15 h.
The invention provides a waste oil treatment catalyst prepared by the preparation method in the technical scheme, which comprises modified silicon dioxide, wherein a hydroxyl functional group and an oxygen functional group are bonded on the surface of the modified silicon dioxide; the particle diameter of the modified silicon dioxide is 20-100 nm, and the specific surface area is 200-600 m 2 /g。
The invention provides the application of the catalyst for waste oil treatment in the technical scheme in waste oil treatment.
The invention provides a waste oil treatment method, which comprises the following steps:
mixing a catalyst with waste oil, and performing catalytic treatment to obtain a treatment product; the catalyst is the catalyst for waste oil treatment in the technical scheme.
The invention provides a preparation method of a catalyst for treating waste oil, which comprises the following steps: mixing water glass, a surfactant, acetic acid and water, and gelatinizing to obtain gel; mixing the gel, the dispersing agent and water, and sequentially dispersing and drying the obtained mixture to obtain silicon dioxide powder; modifying the silicon dioxide powder to obtain a catalyst for treating waste oil; the modification treatment method comprises acid treatment, alkali treatment-sodium borohydride reduction treatment or hydrogen peroxide treatment.
According to the method, water glass is used as a raw material, acetic acid and the water glass are reacted to generate silicic acid colloid, silicon dioxide powder is obtained after drying, silicon dioxide containing-OH or-O can be obtained after modification treatment is carried out on the silicon dioxide powder, functional groups of the catalyst are increased, catalytic activity of the catalyst is increased, impurities in waste oil are intercepted by using a porous structure of the silicon dioxide, the impurities in the waste oil are adsorbed by using hydroxyl and oxygen functional groups contained in the modified silicon dioxide, and oil and impurities in the waste oil are separated through condensation reaction of the increased functional groups and the impurities in the waste oil, so that recycling of the waste oil is realized.
The method has the advantages of rich materials, low cost, energy conservation, environmental protection, simple process and high efficiency.
The method for treating waste oil by using the prepared catalyst has the advantages of excellent waste oil treatment effect, good repeatability, recycling, reduction in cost, increase in resource utilization rate, increase in economic benefit and good industrial application prospect.
Drawings
FIG. 1 TEM image of a catalyst for treating used oil prepared in example 1;
FIG. 2 is a photograph of a used drawing oil as it is;
FIG. 3 is a physical representation of treated used oil obtained during the repeated treatment of 6 used wire drawing oil used oils as they were with the catalyst prepared in example 1;
FIG. 4 is a physical representation of treated used oil obtained during the repeated treatment of 6 used wire drawing oil used oils as they were with the catalyst prepared in example 2;
FIG. 5 is a physical representation of used oil after each treatment obtained during the repeated treatment of 6 used wire drawing oil used oils as they were with the catalyst prepared in example 3;
FIG. 6 is a physical representation of the treated used oil obtained in the process of repeatedly treating 6 used wire drawing oil used oils as they were with the catalyst prepared in example 4;
FIG. 7 is a physical representation of treated used oil obtained during the repeated treatment of 6 used wire drawing oil used oils as they were with the catalyst prepared in example 5;
FIG. 8 is a schematic diagram showing the silica powder prepared in comparative example 1 after treating the wiredrawing waste oil as it is.
Detailed Description
The invention provides a preparation method of a catalyst for treating waste oil, which comprises the following steps:
mixing water glass, a surfactant, acetic acid and water, and gelatinizing to obtain gel;
mixing the gel, a dispersing agent and water, and sequentially dispersing and drying the obtained mixture to obtain silicon dioxide powder;
modifying the silicon dioxide powder to obtain a catalyst for treating waste oil;
the modification treatment method comprises acid treatment, alkali treatment-sodium borohydride reduction treatment or hydrogen peroxide treatment.
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
According to the invention, water glass, a surfactant, acetic acid and water are mixed and gelatinized to obtain gel. The specification of the water glass is not particularly limited in the present invention, and commercially available water glass (Na) well known in the art is used 2 SiO 3 ·9H 2 O) to obtain the product.
In the present invention, the surfactant preferably includes long-chain fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ester, polyoxyethylene alkylamine, polyoxyethylene alkylamide or polyether; more preferably, the surfactant is a polyether, and the polyether is preferably a polyethylene glycol ether. In the present invention, the molar ratio of the water glass to the surfactant is preferably (400 to 2000): 1, more preferably (500 to 1800): 1, more preferably (800 to 1100): 1. the invention utilizes the surfactant to modify the water glass, so that the water glass is fully dispersed in the water.
In the present invention, the amount ratio of the water glass to water is preferably (0.02 to 0.5) mol:100mL, more preferably (0.05 to 0.3) mol:100mL, more preferably 0.06mol:100mL.
In the present invention, the acetic acid is preferably used in the form of an aqueous acetic acid solution, the concentration of which is preferably 0.1 to 2mol/L, more preferably 0.8 to 1.1mol/L; the molar ratio of the acetic acid (acetic acid in the aqueous acetic acid solution) to the water glass is preferably (1 to 2): 1, more preferably (1.2 to 1.8): 1, and still more preferably (1.5 to 1.6): 1.
In the present invention, the process of mixing the water glass, the surfactant, the acetic acid and the water is preferably performed by mixing the water glass and the surfactant, dissolving the mixture in the water, stirring the mixture for 1 hour, and mixing the resulting mixture with the acetic acid. In the present invention, the temperature of the dissolution is preferably 20 to 110 ℃, more preferably 50 to 70 ℃. The stirring speed is not particularly limited in the invention, and the materials can be uniformly mixed according to the process well known in the field.
In the present invention, the temperature of the gelation is preferably 20 to 110 ℃, more preferably 50 to 70 ℃, and the time is preferably 16 to 24 hours, more preferably 18 to 20 hours. During the gelation process, acetic acid reacts with water glass to produce silicic acid colloids.
After the gel is obtained, the gel, the dispersing agent and water are mixed, and the obtained mixture is sequentially dispersed and dried to obtain the silicon dioxide powder. In the present invention, the amount ratio of the gel to water is preferably (1 to 10) g:100mL, more preferably (2 to 8) g:100mL, more preferably (3 to 6) g:100mL.
In the present invention, the dispersant is preferably polyvinylpyrrolidone, polyether derivative or polyethylene glycol, more preferably polyethylene glycol; the concentration of the dispersant in the mixture is preferably 2 to 10mmol/L, more preferably 3 to 8mmol/L, and still more preferably 5 to 6mmol/L. The invention prevents gel agglomeration in the drying process by using the dispersing agent, can reduce the particle size of the final catalyst, is beneficial to increasing the specific surface area of the catalyst, and further improves the adsorption effect of the catalyst on impurities in the waste oil.
In the present invention, the process of mixing the gel, the dispersant and water is preferably to add the gel to the water and then add the dispersant. In the present invention, the dispersion is preferably carried out under stirring conditions; the dispersing time is preferably 4h; the stirring speed is not particularly limited in the invention, and the materials can be uniformly mixed according to the process well known in the field.
In the present invention, the drying temperature is preferably 50 to 130 ℃, more preferably 95 to 110 ℃, and the time is preferably 6 to 15 hours, more preferably 9 to 11 hours. During the drying process, the silicic acid colloid dehydrates to form silicon dioxide.
In the present invention, the silica powder preferably has a particle diameter of 20 to 100nm, more preferably 30 to 50nmnm, and a specific surface area of 400 to 600m 2 (iv) g. The silicon dioxide powder prepared by gelation and dispersion has a porous structure and a functional group (-OH or-O), so that the silicon dioxide powder has a larger specific surface area and the waste oil treatment effect of the catalyst is improved.
After the silicon dioxide powder is obtained, the silicon dioxide powder is modified to obtain the catalyst for treating waste oil. In the invention, the modification treatment method comprises acid treatment, alkali treatment-sodium borohydride reduction treatment or hydrogen peroxide treatment.
In the present invention, the acid treatment reagent is preferably concentrated nitric acid or concentrated sulfuric acid, and the mass fraction of the concentrated nitric acid or the concentrated sulfuric acid is independently preferably 30 to 60%, and more preferably 35 to 45%. In the present invention, the acid treatment is preferably performed by mixing the silica powder with an acid treatment reagent. In the present invention, the amount ratio of the silica powder to the acid treatment agent is preferably (0.5 to 3) g:50mL, more preferably (0.8 to 2.5) g:50mL, more preferably (1.5 to 2.0) g:50mL; the acid treatment is preferably carried out under stirring conditions, and the time for the acid treatment is preferably 6 hours. The rotation speed of the stirring is not particularly limited in the present invention, and may be performed according to a process well known in the art.
In the present invention, the reagent for alkali treatment-sodium borohydride reduction treatment preferably includes an aqueous sodium hydroxide solution and an aqueous sodium borohydride solution; the mass fraction of the sodium hydroxide aqueous solution is preferably 0.05 to 0.3%, more preferably 0.1 to 0.2%; the molar concentration of the sodium borohydride aqueous solution is preferably 0.02 to 0.3mol/L, and more preferably 0.08 to 0.12mol/L. In the present invention, the process of the alkali treatment-sodium borohydride reduction treatment is preferably to mix the silica powder with an aqueous sodium hydroxide solution, perform the alkali treatment, mix the obtained material with the aqueous sodium borohydride solution, and perform the reduction. In the present invention, the ratio of the amount of the silica powder to the amount of the aqueous sodium hydroxide solution is preferably (0.5 to 3) g:50mL, more preferably (0.8-2.5) g:50mL, more preferably (1.5 to 2.0) g:50mL; the dosage ratio of the silicon dioxide powder to the sodium borohydride aqueous solution is preferably (0.1-3) g:20mL, more preferably (0.5 to 2.5) g:20mL, more preferably (1.5 to 2.0) g:20mL.
In the present invention, the time of the alkali treatment is preferably 6 hours; the time for the reduction is preferably 1h. In the present invention, the alkali treatment and the reduction are preferably performed under stirring conditions, and the stirring speed is not particularly limited in the present invention, and may be performed according to a process well known in the art.
In the present invention, the agent for hydrogen peroxide treatment is preferably hydrogen peroxide, and the mass concentration of the hydrogen peroxide is preferably 2 to 20%, and more preferably 4 to 7%. In the present invention, the hydrogen peroxide treatment process is preferably carried out by mixing the silica powder with hydrogen peroxide and oxidizing. In the present invention, the amount ratio of the silica powder to hydrogen peroxide is preferably (0.5 to 3) g:50mL, more preferably (0.8 to 2.5) g:50mL, more preferably (1.5 to 2.0) g:50mL.
In the present invention, the time for the oxidation is preferably 6 hours; the oxidation is preferably carried out under stirring conditions, and the rotation speed of the stirring is not particularly limited in the present invention, and may be carried out according to a process well known in the art.
The invention increases the self functional group of the catalyst through modification treatment, which is beneficial to increasing the catalytic activity of the catalyst.
After the modification treatment is finished, the obtained materials are preferably sequentially filtered and dried to obtain the catalyst for treating the waste oil. The filtration and drying process is not particularly limited in the present invention, and may be performed according to a process well known in the art. In the examples of the present invention, the temperature of the drying was 60 ℃ and the time was 6 hours.
The invention provides a waste oil treatment catalyst prepared by the preparation method in the technical scheme, which comprises modified silicon dioxide, wherein a hydroxyl functional group and an oxygen functional group are bonded on the surface of the modified silicon dioxide; the particle diameter of the modified silicon dioxide is 20-100 nm, and the specific surface area is 200-600 m 2 (iv) g. According to the method, water glass is used as a raw material, acetic acid and the water glass are reacted to generate silicic acid colloid, silicon dioxide powder is obtained after drying, and silicon dioxide containing-OH or-O can be obtained after modification treatment is carried out on the silicon dioxide powder.
The invention provides application of the catalyst for waste oil treatment in the technical scheme in waste oil treatment.
The invention provides a waste oil treatment method, which comprises the following steps:
mixing a catalyst with waste oil, and performing catalytic treatment to obtain a treatment product; the catalyst is the catalyst for waste oil treatment in the technical scheme.
The invention has no special limitation on the type and the source of the waste oil, and the waste oil is obtained according to the method well known in the field; in an embodiment of the invention, the waste oil is in particular hydraulic oil, wire drawing oil, white oil, lubricating oil or cutting oil. The process of mixing the catalyst and the waste oil is not particularly limited in the invention, and the materials can be uniformly mixed according to the process well known in the art. In the invention, the dosage ratio of the catalyst to the waste oil is preferably 10g (100-500) mL, more preferably 10g (200-300) mL; the time of the catalytic treatment is preferably 0.2 to 1 hour, and more preferably 0.5 hour; the temperature of the catalytic treatment is preferably 60 ℃ and the pressure is preferably 5bar.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the 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.
Example 1
0.06mol of water glass (Na) is weighed 2 SiO 3 ·9H 2 O) and 0.06mmol of polyglycol ether (C) 14 H 10 F 17 NO 4 S) mixing, dissolving in 100mL of water, heating to 60 ℃, stirring for 1h, adding 95mL of acetic acid aqueous solution (1 mol/L) into the obtained mixed solution, gelatinizing for 18h, and filtering the obtained product to obtain gel (silicic acid colloid);
adding 100mL of water into 5g of the gel, then adding 0.8mmol of polyethylene glycol, stirring for 4 hours, and drying the obtained product at 105 ℃ for 12 hours to obtain silicon dioxide powder (the particle size is 30-50 nm);
adding 2g of the silicon dioxide powder into 50mL of 0.2 mass percent sodium hydroxide aqueous solution, stirring for 6h, then adding 20mL of 0.1mol/L sodium borohydride aqueous solution, carrying out titration reduction, stirring for 1h, filtering the obtained product, and drying at 60 ℃ for 6h to obtain the catalyst for treating waste oil.
Example 2
0.06mol of water glass (Na) is weighed 2 SiO 3 ·9H 2 O) and 0.06mmol of polyglycol ether (C) 14 H 10 F 17 NO 4 S), mixing the components, dissolving the components in 100mL of water, heating the mixture to 60 ℃, stirring the mixture for 1h, adding 95mL of acetic acid aqueous solution (1 mol/L) into the obtained mixed solution, gelatinizing the mixture for 18h, and filtering the obtained product to obtain gel (silicic acid colloid);
adding 100mL of water into 5g of the gel, then adding 0.8mmol of polyethylene glycol, stirring for 4h, and drying the obtained product at 105 ℃ for 12h to obtain silicon dioxide powder (the particle size is 30-50 nm);
and adding 2g of the silicon dioxide powder into 50mL of hydrogen peroxide with the mass concentration of 5%, stirring for 6h, filtering the obtained product, and drying at 60 ℃ for 6h to obtain the catalyst for treating the waste oil.
Example 3
0.06mol of water glass (Na) is weighed 2 SiO 3 ·9H 2 O) and 0.06mmol of polyglycol ether (C) 14 H 10 F 17 NO 4 S) mixing, dissolving in 100mL of water, heating to 60 ℃, stirring for 1h, adding 95mL of acetic acid aqueous solution (1 mol/L) into the obtained mixed solution, gelatinizing for 18h, and filtering the obtained product to obtain gel (silicic acid colloid);
adding 100mL of water into 5g of the gel, then adding 0.8mmol of polyethylene glycol, stirring for 4 hours, and drying the obtained product at 105 ℃ for 12 hours to obtain silicon dioxide powder (the particle size is 30-50 nm);
and adding 2g of the silicon dioxide powder into 50mL of concentrated nitric acid with the mass concentration of 40%, stirring for 6h, filtering the obtained product, and drying at 60 ℃ for 6h to obtain the catalyst for treating the waste oil.
Example 4
0.06mol of water glass (Na) is weighed 2 SiO 3 ·9H 2 O) and 0.1mmol of polyglycol ether (C) 14 H 10 F 17 NO 4 S) mixing, dissolving in 100mL of water, heating to 60 ℃, stirring for 1h, adding 95mL of acetic acid aqueous solution (1 mol/L) into the obtained mixed solution, gelatinizing for 18h, and filtering the obtained product to obtain gel (silicic acid colloid);
adding 100mL of water into 5g of the gel, then adding 0.8mmol of polyethylene glycol, stirring for 4 hours, and drying the obtained product at 105 ℃ for 12 hours to obtain silicon dioxide powder (the particle size is 30-50 nm);
adding 2g of the silicon dioxide powder into 50mL of 0.2 mass percent sodium hydroxide aqueous solution, stirring for 6h, then adding 20mL of 0.1mol/L sodium borohydride aqueous solution, carrying out titration reduction, stirring for 1h, filtering the obtained product, and drying at 60 ℃ for 6h to obtain the catalyst for treating waste oil.
Example 5
0.06mol of water glass (Na) is weighed 2 SiO 3 ·9H 2 O) and 0.06mmol of polyglycol ether (C) 14 H 10 F 17 NO 4 S) mixing, dissolving in 100mL of water, heating to 60 ℃, stirring for 1h, adding 95mL of acetic acid aqueous solution (1 mol/L) into the obtained mixed solution, gelatinizing for 18h, and filtering the obtained product to obtain gel (silicic acid colloid);
adding 100mL of water into 5g of the gel, then adding 0.4mmol of polyethylene glycol, stirring for 4 hours, and drying the obtained product at 105 ℃ for 12 hours to obtain silicon dioxide powder (the particle size is 30-50 nm);
adding 2g of the silicon dioxide powder into 50mL of 0.2 mass percent sodium hydroxide aqueous solution, stirring for 6h, then adding 20mL of 0.1mol/L sodium borohydride aqueous solution, carrying out titration reduction, stirring for 1h, filtering the obtained product, and drying at 60 ℃ for 6h to obtain the catalyst for treating waste oil.
Comparative example 1
0.06mol of water glass (Na) is weighed 2 SiO 3 ·9H 2 O) and 0.06mmol of polyglycol ether (C) 14 H 10 F 17 NO 4 S), mixing the components, dissolving the components in 100mL of water, heating the mixture to 60 ℃, stirring the mixture for 1h, adding 95mL of acetic acid aqueous solution (1 mol/L) into the obtained mixed solution, gelatinizing the mixture for 18h, and filtering the obtained product to obtain gel (silicic acid colloid);
and adding 100mL of water into 5g of the gel, then adding 0.8mmol of polyethylene glycol, stirring for 4h, and drying the obtained product at 105 ℃ for 12h to obtain silicon dioxide powder (the particle size is 30-50 nm).
Characterization and testing
1) TEM tests were carried out on the treated used oil catalyst prepared in example 1, the results of which are shown in FIG. 1; as can be seen from FIG. 1, the particle size of the catalyst for treating used oil prepared in example 1 was 30 to 50nm.
2) The BET test was carried out on the catalysts prepared in examples 1 to 5, and the results showed that the specific surface area of the catalysts for treating waste oil prepared in examples 1 to 5 was 362.43m in this order 2 /g、323.89m 2 /g、319.12m 2 /g、349.86m 2 G and 351.15m 2 The grain diameter ranges from 30 nm to 50nm.
Application example
10g of the catalysts prepared in examples 1 to 5 and the silica powder prepared in comparative example 1 were respectively filled in a glass tube, 200mL of waste wire drawing oil was then added, the temperature was raised to 60 ℃, pressure was applied at 5bar, so that the waste oil sufficiently passed through the catalysts, catalytic treatment was carried out for 30min, and a treated product was obtained after filtration.
Photographing and observing the process of treating the wire drawing oil waste oil by using the catalysts prepared in examples 1-5 and the silicon dioxide powder prepared in comparative example 1, and the results are shown in figures 2-8; wherein FIG. 2 is a photograph of an intact used wiredrawing oil, and FIGS. 3 to 7 are physical diagrams of treated used oils obtained in the course of repeatedly treating 6 intact used wiredrawing oil oils with the catalysts prepared in examples 1 to 5, respectively (from left to right, the 1 st, 2 nd, 3 rd, 4 th, 5 th and 6 th treated used oils in this order); FIG. 8 is a schematic diagram showing the silica powder prepared in comparative example 1 after treating the wiredrawing waste oil as it is.
As can be seen from the comparison of FIGS. 2 to 7, when the catalysts prepared in examples 1 to 5 were used for treating the waste wiredrawing oil as it is, the color of the treated waste oil became remarkably lighter, i.e., the treatment of the waste oil could be realized; in addition, the catalysts prepared in examples 1-2 and 4-5 still have good treatment effect after being reused for 3-4 times, and the catalyst for treating waste oil prepared by the invention can realize the treatment of waste oil and has good treatment effect.
As is clear from comparison between FIG. 8 and FIGS. 3 to 7, the color of waste oil after the silica powder without modification treatment is still close to that of crude oil, and the treatment of waste oil is not realized.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a catalyst for treating waste oil comprises the following steps:
mixing water glass, a surfactant, acetic acid and water, and gelatinizing to obtain gel;
mixing the gel, the dispersing agent and water, and sequentially dispersing and drying the obtained mixture to obtain silicon dioxide powder;
modifying the silicon dioxide powder to obtain a catalyst for treating waste oil;
the modification treatment method comprises acid treatment, alkali treatment-sodium borohydride reduction treatment or hydrogen peroxide treatment.
2. The method of claim 1, wherein the surfactant comprises a long-chain fatty alcohol polyoxyethylene ether, an alkylphenol polyoxyethylene ether, a fatty acid polyoxyethylene ester, a polyoxyethylene alkylamine, a polyoxyethylene alkylamide, or a polyether.
3. The production method according to claim 1 or 2, wherein the molar ratio of the water glass to the surfactant is (400 to 2000): 1; the molar ratio of the acetic acid to the water glass is (1-2) to 1.
4. The method according to claim 1, wherein the gelation temperature is 20 to 110 ℃ and the time is 16 to 24 hours.
5. The method according to claim 1, wherein the ratio of the amount of the gel to the amount of water is (1 to 10) g:100mL.
6. The method of claim 1, wherein the dispersant is polyvinylpyrrolidone, a polyether derivative, or polyethylene glycol; the concentration of the dispersant in the mixture is 2-10 mmol/L.
7. The production method according to claim 1 or 6, characterized in that the dispersion is carried out under stirring conditions; the dispersing time is 4h; the drying temperature is 50-130 ℃, and the drying time is 6-15 h.
8. A used oil treatment catalyst prepared by the preparation process according to any one of claims 1 to 7, which comprises modified silica having hydroxyl functional groups and oxygen functional groups bonded to the surface thereof; the particle diameter of the modified silicon dioxide is 20-100 nm, and the specific surface area is 200-600 m 2 /g。
9. Use of the used oil treatment catalyst according to claim 8 for treating used oil.
10. A waste oil treatment method is characterized by comprising the following steps:
mixing a catalyst with waste oil, and performing catalytic treatment to obtain a treatment product; the catalyst for waste oil treatment according to claim 8.
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| CN101112991A (en) * | 2006-07-24 | 2008-01-30 | 北京化工大学 | Method for preparing silicon dioxide with large pore volume and large aperture |
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| CN106040203A (en) * | 2016-06-14 | 2016-10-26 | 吉林市润成膜科技有限公司 | Method for preparing modified adsorbent and method for insulating oil waste oil regeneration treatment thereof |
| CN106564906A (en) * | 2016-10-21 | 2017-04-19 | 成都新柯力化工科技有限公司 | Low-cost preparation method for preparation of aerosil by surface modification |
| KR102184315B1 (en) * | 2020-04-02 | 2020-11-30 | 동아대학교산학협력단 | Method for Purifying Waste Working Oil Using Silica Gel and Refining equipment using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101112991A (en) * | 2006-07-24 | 2008-01-30 | 北京化工大学 | Method for preparing silicon dioxide with large pore volume and large aperture |
| CN104492384A (en) * | 2014-12-26 | 2015-04-08 | 重庆工商大学 | Compound type multi-group adsorbing agent for waste oil regeneration |
| CN106040203A (en) * | 2016-06-14 | 2016-10-26 | 吉林市润成膜科技有限公司 | Method for preparing modified adsorbent and method for insulating oil waste oil regeneration treatment thereof |
| CN106564906A (en) * | 2016-10-21 | 2017-04-19 | 成都新柯力化工科技有限公司 | Low-cost preparation method for preparation of aerosil by surface modification |
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Denomination of invention: A catalyst for treating waste oil, its preparation method and application, and waste oil treatment method Granted publication date: 20240524 Pledgee: Bank of Shaoxing Co.,Ltd. high tech Development Zone sub branch Pledgor: Shaoxing Lvyi Technology Development Co.,Ltd. Registration number: Y2024980042976 |