CN115228455B - 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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- CN115228455B CN115228455B CN202110433164.3A CN202110433164A CN115228455B CN 115228455 B CN115228455 B CN 115228455B CN 202110433164 A CN202110433164 A CN 202110433164A CN 115228455 B CN115228455 B CN 115228455B
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- 239000002699 waste material Substances 0.000 title claims abstract description 102
- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 238000011282 treatment Methods 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003921 oil Substances 0.000 claims abstract description 121
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 77
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 30
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 22
- 239000002202 Polyethylene glycol Substances 0.000 claims description 17
- 229920001223 polyethylene glycol Polymers 0.000 claims description 17
- 239000004094 surface-active agent Substances 0.000 claims description 15
- 239000002270 dispersing agent Substances 0.000 claims description 14
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 14
- 239000012279 sodium borohydride Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- 230000009467 reduction Effects 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 10
- 238000001879 gelation Methods 0.000 claims description 10
- -1 polyoxyethylene Polymers 0.000 claims description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 6
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 150000002191 fatty alcohols 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
- 230000008569 process Effects 0.000 abstract description 19
- 239000000377 silicon dioxide Substances 0.000 abstract description 18
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 15
- 239000000084 colloidal system Substances 0.000 abstract description 13
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 9
- 239000012535 impurity Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 8
- 125000000524 functional group Chemical group 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000006482 condensation reaction Methods 0.000 abstract 1
- 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
- 239000000843 powder Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 229910020489 SiO3 Inorganic materials 0.000 description 7
- 238000010306 acid treatment Methods 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000005303 weighing Methods 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
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000007254 oxidation reaction Methods 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
- 239000006185 dispersion Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000010720 hydraulic oil Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000010913 used oil Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 230000006978 adaptation Effects 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
- 239000010730 cutting oil Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- 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, belonging to the technical field of waste oil treatment. According to the invention, water glass is used as a raw material, acetic acid and water glass are used for reacting to generate silicic acid colloid, the silicic acid colloid is dried to obtain silicon dioxide powder, after the silicon dioxide powder is modified, silicon dioxide containing-OH or-O can be obtained, the self functional group of the catalyst is increased, the adsorption effect of the catalyst on impurities in waste oil is increased, and the catalytic treatment of the catalyst on the waste oil is realized through condensation reaction of the increased functional group 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 invention utilizes the prepared catalyst to treat waste oil, has excellent effect of treating waste oil, good repeatability and renewable utilization, and can reduce cost, increase the utilization rate of resources and increase economic benefit.
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 age, industrial oils are increasingly used nowadays, so that a lot of waste oils are produced, for example: hydraulic oil, wire drawing oil, white oil, smooth oil, cutting oil and the like are 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 the waste oil can cause secondary environmental pollution, the resource utilization rate is low, and the resource waste is caused; 2. the waste oil is treated by the oil refining process, but the method has complex process, more equipment and large investment, and is difficult to be suitable for industrialization. Therefore, neither of the above methods is suitable for waste oil treatment.
Currently, environmentally friendly processes of green chemistry are increasingly favored by the chemical industry, and the use of catalysts is one of the main methods of implementing green chemistry. At present, chemical products are treated by the catalyst to reduce environmental pollution, and catalysis plays a vital role in the chemical industry. Therefore, it is important to prepare a catalyst capable of obtaining a waste oil treatment by a simple method, thereby achieving 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 carrying out gelation to obtain gel;
Mixing the gel, the dispersing agent and the water, and dispersing and drying the obtained mixture in sequence to obtain silicon dioxide powder;
Modifying the silicon dioxide powder to obtain a catalyst for treating waste oil;
the modification treatment method is alkali treatment-sodium borohydride reduction treatment or hydrogen peroxide treatment.
Preferably, the surfactant comprises long-chain fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, 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, a step of; the molar ratio of the acetic acid to the water glass is (1-2): 1.
Preferably, the gelation temperature is 20-110 ℃ and the time is 16-24 h.
Preferably, the dosage ratio of the gel to the water is (1-10) g:100mL.
Preferably, the dispersing agent is polyvinylpyrrolidone, polyether derivative or polyethylene glycol; the concentration of the dispersing agent in the mixture is 2-10 mmol/L.
Preferably, the dispersing is performed under stirring conditions; the dispersing time is 4 hours; the drying temperature is 50-130 ℃ and the drying time is 6-15 h.
The invention provides the catalyst for waste oil treatment prepared by the preparation method, 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 size 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 treating waste oil in the technical scheme.
The invention provides a waste oil treatment method, which comprises the following steps:
mixing the catalyst with waste oil, and performing catalytic treatment to obtain a treated product; the catalyst is the catalyst for treating waste oil according to 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 carrying out gelation to obtain gel; mixing the gel, the dispersing agent and the water, and dispersing and drying the obtained mixture in sequence to obtain silicon dioxide powder; modifying the silicon dioxide powder to obtain a catalyst for treating waste oil; the modification treatment method is alkali treatment-sodium borohydride reduction treatment or hydrogen peroxide treatment.
According to the invention, water glass is used as a raw material, acetic acid is used for reacting with water glass to generate silicic acid colloid, silica powder is obtained after drying, silica containing-OH or-O can be obtained after modifying the silica powder, the self functional group of the catalyst is increased, the catalytic activity of the catalyst is increased, impurities in waste oil are intercepted by utilizing the porous structure of the silica, the hydroxyl and oxygen functional groups contained in the modified silica are used for adsorbing the impurities in the waste oil, and the increased functional groups are used for condensing with the impurities in the waste oil to separate oil and impurities in the waste oil, so that the recycling of the waste oil is realized.
The method has the advantages of abundant materials, low cost, energy conservation, environmental protection, simple process and high efficiency.
The method for treating the waste oil by using the prepared catalyst has the advantages of excellent effect, good repeatability, renewable utilization, reduced cost, increased resource utilization rate, increased economic benefit and good application prospect in industry.
Drawings
FIG. 1 is a TEM image of a catalyst for treating waste oil prepared in example 1;
FIG. 2 is a photograph of the used oil of the drawing oil as it is in the application example;
FIG. 3 is a physical diagram of the treated waste oil obtained in the course of repeatedly treating 6 wire drawing oil waste oils as they are with the catalyst prepared in example 1;
FIG. 4 is a physical diagram of the treated waste oil obtained in the course of repeatedly treating 6 wire drawing oil waste oils with the catalyst prepared in example 2 as it is;
FIG. 5 is a physical diagram of the treated waste oil obtained in each of the procedures of repeating the treatment of 6 wire drawing oil waste oils with the catalyst prepared in example 3;
FIG. 6 is a physical diagram of the treated waste oil obtained in the course of repeatedly treating 6 wire drawing oil waste oils with the catalyst prepared in example 4 as it is;
FIG. 7 is a physical diagram of the treated waste oil obtained in the course of repeatedly treating 6 wire drawing oil waste oils with the catalyst prepared in example 5 as it is;
FIG. 8 is a physical diagram of the silica powder prepared in comparative example 1 after the wire drawing waste oil was treated 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 carrying out gelation to obtain gel;
Mixing the gel, the dispersing agent and the water, and dispersing and drying the obtained mixture in sequence to obtain silicon dioxide powder;
Modifying the silicon dioxide powder to obtain a catalyst for treating waste oil;
the modification treatment method is alkali treatment-sodium borohydride reduction treatment or hydrogen peroxide treatment.
In the present invention, the preparation materials are commercially available as known to those skilled in the art unless otherwise specified.
The invention mixes water glass, surfactant, acetic acid and water to gel, and the gel is obtained. The specific specification of the water glass is not particularly limited, and commercially available water glass (Na 2SiO3·9H2 O) well known in the art may be used.
In the present invention, the surfactant preferably includes a long-chain fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ester, polyoxyethylene alkylamine, polyoxyethylene alkylamide, or polyether; the surfactant is more preferably a polyether, 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 water.
In the present invention, the water glass to water ratio 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 acetic acid (acetic acid in acetic acid aqueous solution) to 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 to mix the water glass with the surfactant, dissolve in the water, stir for 1h, and mix the obtained 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, and the materials can be uniformly mixed according to the process well known in the art.
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 colloid.
After the gel is obtained, the gel, the dispersing agent and the water are mixed, and the obtained mixture is dispersed and dried in sequence to obtain the silicon dioxide powder. In the present invention, the ratio of the gel to the water is preferably (1 to 10) g:100mL, more preferably (2-8) g:100mL, more preferably (3-6) g:100mL.
In the present invention, the dispersant is preferably polyvinylpyrrolidone, a 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 uses the dispersing agent to prevent gel agglomeration in the drying process, 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 waste oil.
In the present invention, the process of mixing the gel, the dispersant and the water is preferably to add the gel to the water and then to add the dispersant. In the present invention, the dispersion is preferably carried out under stirring; the dispersed the time is preferably 4 hours; the stirring speed is not particularly limited, and the materials can be uniformly mixed according to the process well known in the art.
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 is dehydrated to form silica.
In the present invention, the particle diameter of the silica powder is preferably 20 to 100nm, more preferably 30 to 50nm, and the specific surface area is preferably 400 to 600m 2/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 improves the waste oil treatment effect of the catalyst.
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 concentrated sulfuric acid is preferably 30 to 60% by mass, more preferably 35 to 45% by mass. 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 ratio of the amount of the silica powder to the amount of 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, and the acid treatment time is preferably 6 hours. The rotational 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.
In the present invention, the alkali treatment-sodium borohydride reduction treatment agent preferably includes an aqueous sodium hydroxide solution and an aqueous sodium borohydride solution; the mass fraction of the aqueous sodium hydroxide 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, more preferably 0.08 to 0.12mol/L. In the present invention, the alkali treatment-sodium borohydride reduction treatment is preferably carried out by mixing a silica powder with an aqueous sodium hydroxide solution, carrying out alkali treatment, mixing the obtained material with an aqueous sodium borohydride solution, and carrying out reduction. In the present invention, the ratio of the amount of the silica powder to the aqueous sodium hydroxide solution 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 ratio of the amount of the silica powder to the sodium borohydride aqueous solution is preferably (0.1 to 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 of the reduction is preferably 1h. In the present invention, the alkali treatment and the reduction are preferably performed under stirring conditions, and the rotation speed of the stirring is not particularly limited, and may be performed according to a process well known in the art.
In the invention, the reagent for hydrogen peroxide treatment is preferably hydrogen peroxide, and the mass concentration of the hydrogen peroxide is preferably 2-20%, more preferably 4-7%. In the invention, the hydrogen peroxide treatment process is preferably to mix silicon dioxide powder with hydrogen peroxide for oxidization. In the invention, the dosage ratio of the silicon dioxide powder to the hydrogen peroxide is preferably (0.5-3) 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 of 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 functional group of the catalyst by modifying treatment, which is beneficial to increasing the catalytic activity of the catalyst.
After the modification treatment is completed, the obtained materials are preferably filtered and dried in sequence, so that the catalyst for treating the waste oil is obtained. The process of filtering and drying is not particularly limited in the present invention, and may be performed according to a process well known in the art. In an embodiment of the invention, the drying temperature is 60 ℃ and the drying time is 6 hours.
The invention provides the catalyst for waste oil treatment prepared by the preparation method, 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 size of the modified silicon dioxide is 20-100 nm, and the specific surface area is 200-600 m 2/g. According to the invention, water glass is used as a raw material, acetic acid and water glass are used for reacting to generate silicic acid colloid, and the silicic acid colloid is dried to obtain silicon dioxide powder, and after the silicon dioxide powder is modified, silicon dioxide containing-OH or-O can be obtained, and the modified silicon dioxide has a strong adsorption effect on impurities in waste oil and a weak adsorption effect on oil, so that the waste oil is treated.
The invention provides the application of the catalyst for treating waste oil in the technical scheme.
The invention provides a waste oil treatment method, which comprises the following steps:
mixing the catalyst with waste oil, and performing catalytic treatment to obtain a treated product; the catalyst is the catalyst for treating waste oil according to the technical scheme.
The invention is not particularly limited in the kind and source of the waste oil, and the waste oil can be obtained according to a method well known in the art; in an embodiment of the present invention, the waste oil is specifically hydraulic oil, wire drawing oil, white oil, smooth oil or chip oil. The process of mixing the catalyst with the waste oil is not particularly limited in the present invention, and the materials may be uniformly mixed according to a process well known in the art. In the present invention, the ratio of the catalyst to the used 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, more preferably 0.5 hour; the temperature of the catalytic treatment is preferably 60℃and the pressure is preferably 5bar.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Weighing 0.06mol of water glass (Na 2SiO3·9H2 O) and 0.06mmol of polyethylene glycol ether, mixing with each other, 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 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 (particle size of 30-50 nm);
2g of the silicon dioxide powder is added into 50mL of sodium hydroxide aqueous solution with mass concentration of 0.2%, stirring is carried out for 6h, then 20mL of sodium borohydride aqueous solution with mass concentration of 0.1mol/L is added, titration reduction is carried out, stirring is carried out for 1h, the obtained product is filtered, and drying is carried out at 60 ℃ for 6h, thus obtaining the catalyst for treating waste oil.
Example 2
Weighing 0.06mol of water glass (Na 2SiO3·9H2 O) and 0.06mmol of polyethylene glycol ether, mixing with each other, 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 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 (particle size of 30-50 nm);
And adding 2g of the silicon dioxide powder into 50mL of hydrogen peroxide with mass concentration of 5%, stirring for 6h, filtering the obtained product, and drying at 60 ℃ for 6h to obtain the catalyst for treating waste oil.
Example 3
Weighing 0.06mol of water glass (Na 2SiO3·9H2 O) and 0.06mmol of polyethylene glycol ether, mixing with each other, 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 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 (particle size of 30-50 nm);
2g of the silicon dioxide powder is added into 50mL of concentrated nitric acid with mass concentration of 40%, the mixture is stirred for 6 hours, the obtained product is filtered, and then the product is dried for 6 hours at 60 ℃ to obtain the catalyst for treating waste oil.
Example 4
0.06Mol of water glass (Na 2SiO3·9H2 O) and 0.1mmol of polyethylene glycol ether are weighed and mixed with each other, dissolved in 100mL of water, heated to 60 ℃, stirred for 1h, 95mL of acetic acid aqueous solution (1 mol/L) is added into the obtained mixed solution, gelation is carried out for 18h, and the obtained product is filtered to obtain gel (silicic acid colloid);
adding 100mL of water into 5g of 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 (particle size of 30-50 nm);
2g of the silicon dioxide powder is added into 50mL of sodium hydroxide aqueous solution with mass concentration of 0.2%, stirring is carried out for 6h, then 20mL of sodium borohydride aqueous solution with mass concentration of 0.1mol/L is added for titration reduction, stirring is carried out for 1h, the obtained product is filtered, and then drying is carried out at 60 ℃ for 6h, thus obtaining the catalyst for treating waste oil.
Example 5
Weighing 0.06mol of water glass (Na 2SiO3·9H2 O) and 0.06mmol of polyethylene glycol ether, mixing with each other, 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 gel, then adding 0.4mmol of polyethylene glycol, stirring for 4h, and drying the obtained product at 105 ℃ for 12h to obtain silicon dioxide powder (particle size of 30-50 nm);
2g of the silicon dioxide powder is added into 50mL of sodium hydroxide aqueous solution with mass concentration of 0.2%, stirring is carried out for 6h, then 20mL of sodium borohydride aqueous solution with mass concentration of 0.1mol/L is added for titration reduction, stirring is carried out for 1h, the obtained product is filtered, and then drying is carried out at 60 ℃ for 6h, thus obtaining the catalyst for treating waste oil.
Comparative example 1
Weighing 0.06mol of water glass (Na 2SiO3·9H2 O) and 0.06mmol of polyethylene glycol ether, mixing with each other, 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);
To 5g of the gel, 100mL of water was added, followed by 0.8mmol of polyethylene glycol, stirring was performed for 4 hours, and the resultant product was dried at 105℃for 12 hours to obtain a silica powder (particle diameter: 30 to 50 nm).
Characterization and testing
1) TEM test was performed on the catalyst for treating waste oil prepared in example 1, and the results are shown in FIG. 1; as is clear from FIG. 1, the particle size of the catalyst for treating waste oil prepared in example 1 is 30 to 50nm.
2) BET tests were carried out on the catalysts prepared in examples 1 to 5, and the results showed that the specific surface areas of the catalysts for treating waste oil prepared in examples 1 to 5 were 362.43m 2/g、323.89m2/g、319.12m2/g、349.86m2/g and 351.15m 2/g, respectively, and the particle size ranges were 30to 50nm.
Application example
10G of the catalyst prepared in examples 1 to 5 and the silica powder prepared in comparative example 1 were respectively filled in a glass tube, 200mL of wire drawing oil waste oil was then added, the temperature was raised to 60℃and the pressure was 5bar so that the waste oil was allowed to pass through the catalyst sufficiently, and the catalyst was subjected to catalytic treatment for 30 minutes, and after filtration, a treated product was obtained.
Photographing and observing the process of treating the wiredrawing oil waste oil by using the catalysts prepared in examples 1 to 5 and the silicon dioxide powder prepared in comparative example 1, and the results are shown in fig. 2 to 8; wherein, FIG. 2 is a photograph of the wire drawing oil waste oil as it is, and FIGS. 3 to 7 are respectively physical diagrams of the treated waste oil (waste oil after 1 st, 2 nd, 3 rd, 4 th, 5 th and 6 th treatments in order from left to right) obtained in the course of repeating 6 wire drawing oil waste oils as it is with the catalyst prepared in examples 1 to 5; FIG. 8 is a physical diagram of the silica powder prepared in comparative example 1 after the wire drawing waste oil was treated as it is.
As can be seen from comparison of fig. 2 to 7, the catalysts prepared in examples 1 to 5 were used for treating the wire drawing oil waste oil as it is, and the color of the treated waste oil product became significantly lighter, i.e. the waste oil treatment could be realized; in addition, after the catalysts prepared in examples 1-2 and 4-5 are reused for 3-4 times, the catalyst still has a good treatment effect, and the catalyst for treating waste oil prepared by the method can realize treatment of waste oil and has a good treatment effect.
As is clear from comparison between fig. 8 and fig. 3 to 7, the color of the waste oil after the treatment of the silica powder without the modification treatment is still close to that of the crude oil, and the treatment of the waste oil is not realized.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. A method for preparing a catalyst for treating waste oil, comprising the steps of:
Mixing water glass, a surfactant, acetic acid and water, and carrying out gelation to obtain gel;
Mixing the gel, the dispersing agent and the water, and dispersing and drying the obtained mixture in sequence to obtain silicon dioxide powder;
Modifying the silicon dioxide powder to obtain a catalyst for treating waste oil;
the modification treatment method is alkali treatment-sodium borohydride reduction treatment or hydrogen peroxide treatment;
the surfactant is long-chain fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ester, polyoxyethylene alkylamine, polyoxyethylene alkylamide or polyether.
2. The preparation method according to claim 1, wherein 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): 1.
3. The method according to claim 1, wherein the gelation temperature is 20 to 110 ℃ and the time is 16 to 24 hours.
4. The method according to claim 1, wherein the ratio of the gel to the water is (1-10) g/100 mL.
5. The preparation method according to claim 1, wherein the dispersant is polyvinylpyrrolidone, a polyether derivative or polyethylene glycol; the concentration of the dispersing agent in the mixture is 2-10 mmol/L.
6. The method of claim 1 or 5, wherein the dispersing is performed under stirring; the dispersing time is 4 hours; the drying temperature is 50-130 ℃ and the drying time is 6-15 h.
7. The catalyst for waste oil treatment prepared by the preparation method of any one of claims 1 to 6, which comprises modified silica, wherein a hydroxyl functional group and an oxygen functional group are bonded to the surface of the modified silica; the particle size of the modified silicon dioxide is 20-100 nm, and the specific surface area is 200-600 m 2/g.
8. Use of the catalyst for treating waste oil according to claim 7 for treating waste oil.
9. A method for treating waste oil, comprising the steps of:
Mixing the catalyst with waste oil, and performing catalytic treatment to obtain a treated product; the catalyst is the catalyst for treating waste oil according to claim 7.
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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 |
| 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 |
| 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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Patent Citations (5)
| 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 |
| 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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