CN109593575B - Preparation method of cerium-based nano material - Google Patents
Preparation method of cerium-based nano material Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/12—Inorganic compounds
- C10L1/1233—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof
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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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/188—Carboxylic acids; metal salts thereof
- C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
Abstract
The invention discloses a preparation method of a cerium-based nano material, wherein the cerium-based nano material is prepared by a micro-channel reactor, and the micro-channel reactor at least comprises a section I, a section II, a section III and a section IV which are sequentially connected along the flow direction of a solution; the preparation method comprises the following steps: carrying out precipitation reaction in the section I; carrying out oxidation reaction in the stage II; dispersing in stage III; modifying long-chain organic acid and dissolving in oil in the section IV; and finally, collecting the reaction solution in the microchannel reactor, standing for layering, and taking an oil phase to obtain the catalyst. The invention adopts the microchannel reactor for reaction control, can realize continuous production, shortens the reaction time (the retention time of the solution in the reactor is 40-110s), and improves the stability of the process; meanwhile, the sediment solid is dispersed by the dispersing agent, and the sediment is prevented from being blocked in the microchannel reactor by combining the control of the liquid flow rate.
Description
Technical Field
The invention belongs to the field of fuel additives, and particularly relates to a preparation method of a cerium-based diesel additive by adopting a microchannel reactor.
Background
Diesel engines have exhaust emissions containing primarily nitrogen oxides and PM particulates due to the oxygen-rich and non-uniform combustion characteristics of diesel fuel in combustion chambers. The common diesel additive products in various markets, including pour point depressant, stabilizer, emulsifier, detergent and cetane number improver, are added to improve the oil qualityThe combustion is promoted, the fuel economy is improved, but the actual influence on the exhaust pollutant emission is small. Nano cerium oxide (CeO)2) The valence state of the medium cerium is variable, and the medium cerium. The cerium-based diesel additive can reduce the emission of PM particles in the tail gas of a diesel engine, prevent the enrichment of PM in a particle catcher in a tail gas aftertreatment pipeline, and reduce the air resistance of the tail gas pipeline, thereby achieving the energy-saving effect of reducing oil consumption. In the european and north american regions, it has been widely used for nearly 20 years. Foreign products include Envirox in the United kingdom, Eolys in Rodia, France, and Pt Plus from clean Diesel company, USA. China still belongs to a blank in the product field.
The organic acid cerium salt is directly added into the diesel oil to reduce the concentration of particulate matters in the tail gas, but the organic acid cerium salt is not suitable for the use requirement of actual long-term storage in the diesel oil. Chinese patent CN102101691B reports that a nano cerium oxide material which can form stable dispersion in nonpolar oil is prepared by adopting a supergravity device, but the batch charging amount is large, the device investment is high, the occupied area is large, and the energy consumption is high. Foreign patents WO 03/040270A2 and US7459484B2 disclose methods for preparing metal oxide nano-material diesel additives by adopting a multi-step batch process, but the method has multiple steps, long time and low production efficiency.
The intermolecular reaction mass transfer speed in the microchannel reactor is accelerated, the reaction temperature control is more accurate, the mass transfer and heat transfer processes are enhanced, the reaction time can be greatly reduced to the second or minute level, the defect that the concentration of reactants in a kettle type reactor changes along with the reaction time is avoided, the process is stable, and the batch stability of products is high. However, solid precipitates are generated in the preparation process of the cerium-based nano material, and the pipeline of the microchannel reactor is easy to be blocked by adopting the microchannel reactor.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation process of a cerium-based diesel additive, which can realize continuous production, has short reaction time and is stable and controllable in process.
In order to achieve the above object, the present invention provides a method for preparing a cerium-based nanomaterial, wherein the cerium-based nanomaterial is prepared by a microchannel reactor, and the microchannel reactor at least comprises a section I, a section II, a section III and a section IV which are sequentially connected in the solution flowing direction; the preparation method specifically comprises the following steps:
(1) a precipitation step: respectively pumping a soluble cerium salt aqueous solution and an alkaline aqueous solution into a section I of the microchannel reactor from an inlet of the section I for precipitation reaction, controlling the pumping speed of the solutions to ensure that the stroke time of the mixed solution of the cerium salt aqueous solution and the alkaline aqueous solution in the section I is 5-35s, and controlling the reaction temperature in the section I to be 0-50 ℃;
(2) an oxidation step: pumping an oxidant into an inlet of the II section of the microchannel reactor, aiming at oxidizing the + 3-valent cerium into + 4-valent cerium;
(3) a dispersing step: pumping a dispersant solution into an inlet of a section III of the microchannel reactor;
(4) oil dissolving step: pumping an oil phase solution of long-chain organic acid into an inlet of an IV section of the microchannel reactor for modification reaction, controlling the pumping speed of the oil phase solution to ensure that the stroke time of the mixed solution in the IV section is 15-55s, and controlling the reaction temperature in the IV section to be 50-90 ℃;
(5) and collecting the reaction solution in the microchannel reactor, standing for 12-24h, and layering to obtain an oil phase which is the cerium-based nano material solution.
And (2) continuously pumping the water solution and the alkaline water solution of the soluble cerium salt in the step (1), the oxidant in the step (2), the dispersant in the step (3) and the oil phase solution of the long-chain organic acid in the step (4) until the preparation process is finished.
Wherein the pumping speed of the solution in each step is controlled so that the molar ratio of the soluble cerium salt to the dispersant pumped in unit time is 100: 5-80.
Further, the pumping speed of the solution in each step is controlled, so that the molar ratio of the soluble cerium salt, the oxidant, the dispersant and the long-chain organic acid pumped in unit time is 100: 45-55: 5-80: 35-80, preferably in a molar ratio of 100: 50: 63: 70.
wherein the soluble cerium salt is cerium nitrate or cerium acetate (with concentration of 0.01-1.5mol/L, preferably 0.1-0.7 mol/L); the alkaline aqueous solution is ammonia water or sodium hydroxide aqueous solution (with concentration of 0.01-2mol/L, preferably 0.1-0.7 mol/L); the oxidant is hydrogen peroxide or hypochlorite; the dispersant is one or more of sodium dodecyl benzene sulfonate, acetic acid, polyethylene glycol with molecular weight of 800-; the long-chain organic acid adopts saturated fatty acid of C8-C18; the oil phase solution adopts long-chain aliphatic hydrocarbon solvent D60 or D80. Preferably, the concentration of the long-chain organic acid in the oil phase solution of the long-chain organic acid is 5 wt%.
Further, the temperature in the section I in the step (1) is preferably controlled at 10-20 ℃; the temperature of the second section in the step (2) is controlled to be 25-35 ℃; controlling the temperature of the section III in the step (3) to be 25-35 ℃; the temperature of the IV section in the step (4) is preferably controlled to be 70-80 ℃.
Preferably, the pumping speed of the oxidant in the step (2) is controlled so that the travel time of the mixed solution in the section II is 5-15 s; and (3) controlling the pumping speed of the dispersant solution in the step (3) to ensure that the travel time of the mixed solution in the section III is 5-15 s.
Compared with the prior art, the invention has the following advantages:
the invention adopts the microchannel reactor for reaction control, can realize continuous production, shortens the reaction time (the total retention time of the solution in the reactor is 40-110s), and improves the stability of the process.
The invention disperses the precipitated solid by the dispersant, and avoids the blockage of the sediment to the microchannel reactor by combining the control of the liquid flow rate; meanwhile, long-chain organic acid is used for modifying the nano cerium hydroxide prepared after precipitation and oxidation, so that the nano cerium hydroxide can stably exist in the oil phase solution.
The cerium-based nano material oil phase solution prepared by the invention can be used as a diesel additive, can effectively catalyze and reduce the ignition temperature of diesel, effectively reduce the emission of particulate matters in the tail gas of a diesel engine, and can be stably stored for 1.5 years without agglomeration and precipitation of the oil phase solution.
Drawings
FIG. 1 is a transmission electron micrograph of a cerium-based nanomaterial in an oily sample prepared in example 1 of the present invention;
FIG. 2 is a graph showing the measurement of the particle size distribution of cerium-based nanomaterial in an oily sample prepared in example 1 of the present invention;
fig. 3 is an XRD chart of the powder obtained by evaporating the oily sample prepared in examples 1 and 2 of the present invention;
fig. 4 is a comparison spectrum of temperature programming oxidation of fine powder, which is obtained by evaporating an oily sample prepared by each embodiment of the present invention to dryness, in an oxygen-argon mixed atmosphere after the fine powder is ground and mixed with carbon powder;
in fig. 4, the peak top temperature is the oxygen consumption peak when carbon in the mixed sample is combusted, i.e., the light-off temperature after carbon is mixed with cerium oxide;
FIG. 5 is a graph showing the comparison between the oily sample obtained in example 1 of the present invention and the commercially available national No. 0 diesel fuel (Ce content in diesel fuel 15ppm) and the tail gas smoke density of a conventional diesel engine (filter paper smoke detector, engine speed 2800r/min as test conditions).
Detailed Description
The present invention will be described in detail with reference to specific examples.
The microchannel reactor used in the following examples had an internal tube diameter of 0.1 to 6 mm.
Example 1
A precipitation step: pumping 0.15mol/L cerium acetate aqueous solution and 0.2mol/L ammonia water into the I section of the microchannel reactor at constant flow rates of 18ml/min and 49ml/min respectively, and mixing for precipitation reaction. The travel time of the mixed solution in the section I is 7.2s, the reaction temperature is 15 ℃, and the pH value of the system after the reaction is 8.
An oxidation step: and pumping 10 wt% hydrogen peroxide solution into the second section of the microchannel reactor at the flow rate of 0.5 ml/min. The travel time of the total mixed solution pumped with the hydrogen peroxide in the section II is 7.1s, and the temperature in the section II is controlled to be 30 ℃.
A dispersing step: 1mol/L acetic acid water solution is pumped into the III section of the microchannel reactor, and the flow rate is 1.7 ml/min. The total mixed solution after the acetic acid was pumped in section III for a 6.9s time and the temperature in section III was controlled at 30 ℃.
Oil dissolving step: d80 aviation kerosene solution of isooctanoic acid was pumped into the IV stage of the microchannel reactor at a concentration of 5 wt% and a pumping rate of 6.8 ml/min. The total mixed solution after the pumping of the organic acid had a stroke time of 25.3s in the section IV and the reaction temperature in the section IV was controlled to 75 ℃.
And continuously pumping the raw materials in each step according to a preset flow rate until all the raw materials corresponding to the product cerium-based nano material with the required preparation amount in the production stage are pumped.
And (3) collecting the mixed solution after the reaction of the microchannel reactor is finished, standing the obtained mixed solution for 16h for liquid separation, wherein the oil phase contains the cerium-based nano material and can be used for a diesel additive.
In this example, the molar ratio of the soluble cerium salt, the oxidant, the dispersant and the long-chain organic acid pumped in a unit time is 100: 50: 63: 70.
the molar content of Ce in the final oil phase product was 0.053 g/mL.
The oil phase sample prepared in this example was taken for cerium-based nanomaterial detection: as can be seen from the TEM image of FIG. 1, the obtained cerium-based nanomaterial has a particle size of approximately 8-15 nm. FIG. 2 is a graph showing a particle size distribution test of the cerium-based nanomaterial obtained in example 1, with an average particle size of 14 nm.
It can be comprehensively seen from fig. 1 and 2 that the particle size of the cerium-based material in the obtained oil phase sample is in the nanometer level, and the particle size distribution is uniform and concentrated without obvious agglomeration.
Example 2
A precipitation step: 0.4mol/L cerous nitrate aqueous solution and 0.1mol/L ammonia water are respectively pumped into the I section of the microchannel reactor at constant flow rates of 3ml/min and 48ml/min to be mixed for precipitation reaction. The travel time of the mixed solution in the section I is 28.2s, the reaction temperature is 0 ℃, and the pH value of the system after the reaction is 10.
An oxidation step: and pumping 0.5mol/L sodium hypochlorite aqueous solution into the II section of the microchannel reactor at the flow rate of 1.2 ml/min. The total mixed solution after the pumping of sodium hypochlorite had a stroke time of 9.2s in stage II, and the temperature in stage II was controlled at 15 ℃.
A dispersing step: 0.2mol/L ethanolamine aqueous solution is pumped into the III section of the microchannel reactor at the flow rate of 2.7 ml/min. The total mixed solution after the ethanolamine pumping was run for 8.7s in stage III, and the temperature in stage III was controlled to 45 ℃.
In the oil dissolving step: into the IV stage of the microchannel reactor, tetradecanoic acid in D80 aviation kerosene was pumped at a concentration of 5 wt% and a pumping rate of 4.4 ml/min. The total mixed solution after the pumping of the organic acid had a stroke time of 48.6s in the section IV and the reaction temperature in the section IV was controlled to 55 ℃.
And continuously pumping the raw materials in each step according to a preset flow rate until all the raw materials corresponding to the product cerium-based nano material with the required preparation amount in the production stage are pumped.
And (3) collecting the mixed solution after the reaction of the microchannel reactor is finished, standing the obtained mixed solution for 13h for liquid separation, wherein the oil phase contains the cerium-based nano material and can be used for a diesel additive.
In this example, the molar ratio of the soluble cerium salt, the oxidant, the dispersant and the long-chain organic acid pumped in a unit time is 100: 50: 45: 65.
the molar content of Ce in the final oil phase product was 0.036 g/mL.
The oil phase sample prepared in this example was taken for cerium-based nanomaterial detection: as can be seen from a transmission electron microscope picture, the grain size distribution of the cerium-based nano material is between 13 and 23 nm; as can be seen from the particle size distribution measurement, the average particle size of the cerium-based nanomaterial is 20 nm.
The cerium-based material in the oil phase sample prepared by the embodiment has a nano-grade particle size, uniform and concentrated particle size distribution and no obvious agglomeration phenomenon.
Example 3
A precipitation step: 0.7mol/L cerous nitrate aqueous solution and 0.7mol/L ammonia water are respectively pumped into the I section of the microchannel reactor at a constant flow rate of 10ml/min and 34.5ml/min for mixing and carrying out precipitation reaction. The travel time of the mixed solution in the section I is 10.8s, the reaction temperature is 45 ℃, and the pH value of the system after the reaction is 7.
An oxidation step: 10 wt% hydrogen peroxide solution was pumped into stage II of the microchannel reactor at a flow rate of 1.2 ml/min. The travel time of the total mixed solution pumped with the hydrogen peroxide in the section II is 10.5s, and the temperature in the section II is controlled to be 45 ℃.
A dispersing step: 10 wt% sodium dodecylbenzenesulfonate aqueous solution was pumped into the third stage of the microchannel reactor at a flow rate of 2.2 ml/min. The total mixed solution after the dispersant was pumped in the section III was allowed to travel for 10s, and the temperature in the section III was controlled at 15 ℃.
In the oil dissolving step: d80 aviation kerosene solution of isostearic acid with the concentration of 5 wt% was pumped into the IV section of the microchannel reactor at the pumping speed of 26.4 ml/min. The total mixed solution after the pumping of the organic acid had a stroke time of 19.4s in the section IV and the reaction temperature in the section IV was controlled to 85 ℃.
And continuously pumping the raw materials in each step according to a preset flow rate until all the raw materials corresponding to the product cerium-based nano material with the required preparation amount in the production stage are pumped.
And (3) collecting the mixed solution after the reaction of the microchannel reactor is finished, standing the obtained mixed solution for 16h for liquid separation, wherein the oil phase contains the cerium-based nano material and can be used for a diesel additive.
In this example, the molar ratio of the soluble cerium salt, the oxidant, the dispersant and the long-chain organic acid pumped in a unit time is 100: 50: 10: 53.
the molar content of Ce in the final oil phase product was 0.035 g/mL.
The oil phase sample prepared in this example was taken for cerium-based nanomaterial detection: as can be seen from a transmission electron microscope picture, the grain size distribution of the cerium-based nano material is between 20 and 31 nm; as can be seen from the particle size distribution measurement, the average particle size of the cerium-based nanomaterial is 28 nm.
The cerium-based material in the oil phase sample prepared by the embodiment has a nano-grade particle size, uniform and concentrated particle size distribution and no obvious agglomeration phenomenon.
Example 4
A precipitation step: 0.1mol/L cerium acetate aqueous solution and 0.1mol/L sodium hydroxide are respectively pumped into the I section of the microchannel reactor at a constant flow rate of 10ml/min and 31.3ml/min for mixing and carrying out precipitation reaction. The travel time of the mixed solution in the section I is 23.2s, the reaction temperature is 40 ℃, and the pH value of the system after the reaction is 8.5.
An oxidation step: 10 wt% hydrogen peroxide solution was pumped into stage II of the microchannel reactor at a flow rate of 0.2 ml/min. The travel time of the total mixed solution pumped with the hydrogen peroxide in the section II is 11.6s, and the temperature in the section II is controlled to be 30 ℃.
A dispersing step: 20 wt% of polyethylene glycol (molecular weight 800) in ethanol was pumped into section III of the microchannel reactor at a flow rate of 1.4 ml/min. The total mixed solution after the dispersant was pumped in section III was allowed to travel for 11.2s and the temperature in section III was controlled at 30 ℃.
In the oil dissolving step: d60 aviation kerosene solution of isooctanoic acid was pumped into the IV stage of the microchannel reactor at a concentration of 5 wt% and a pumping rate of 1.6 ml/min. The total mixed solution after the pumping of the organic acid had a stroke time of 32.4s in the section IV and the reaction temperature in the section IV was controlled to 85 ℃.
And continuously pumping the raw materials in each step according to a preset flow rate until all the raw materials corresponding to the product cerium-based nano material with the required preparation amount in the production stage are pumped.
And (3) collecting the mixed solution after the reaction of the microchannel reactor is finished, standing the obtained mixed solution for 20h for liquid separation, wherein the oil phase contains the cerium-based nano material and can be used for a diesel additive.
In this example, the molar ratio of the soluble cerium salt, the oxidant, the dispersant and the long-chain organic acid pumped in a unit time is 100: 50: 35: 45.
the molar content of Ce in the final oil phase product was 0.083 g/mL.
Taking the oil phase sample prepared in the embodiment to perform cerium-based nano material detection: as can be seen from a transmission electron microscope picture, the grain size distribution of the cerium-based nano material is between 25 and 40 nm; as can be seen from the particle size distribution measurement, the average particle size of the cerium-based nanomaterial was 33 nm.
The cerium-based material in the oil phase sample prepared by the embodiment has a nano-grade particle size, uniform and concentrated particle size distribution and no obvious agglomeration phenomenon.
Effects of the embodiment
The oily samples obtained in examples 1 and 2 were evaporated to dryness at 500 ℃ to obtain cerium oxide powder. The powder XRD patterns corresponding to the oil samples of examples 1 and 2 are shown in FIG. 3. The cerium-based nano material oil sample obtained by the method can form cerium oxide after being heated, wherein the broadening of the XRD peak shape obviously indicates that the cerium oxide is nano-scale cerium oxide.
The oil sample in each example is evaporated to dryness to obtain nanometer cerium oxide powder, the nanometer cerium oxide powder and certain carbon powder are ground and mixed (the mixing ratio is 4:1) in oxygen argon (O)2a/Ar, 10%) mixed atmosphere, as shown in fig. 4, for temperature programmed oxidation (compare to pure carbon powder). Wherein the peak shape corresponds to the oxygen consumption of carbon powder combustion, and the peak top temperature corresponds to the ignition temperature after carbon and cerium oxide are mixed. The oily sample obtained by the method can reduce the ignition temperature of the carbon powder by catalytic oxidation, and the product obtained by the embodiment 1 of the invention has the optimal effect.
The oily sample obtained in example 1 was mixed with a commercially available national diesel fuel No. 0 (the Ce content in diesel fuel is 15ppm) and compared with the tail gas smoke density of a conventional diesel engine (a filter paper smoke meter, and the engine speed 2800r/min is used as a test condition), as shown in fig. 5. The oily product obtained by the invention can be used as a diesel additive to effectively reduce the emission of particulate matters in the tail gas of a diesel engine.
Claims (6)
1. A preparation method of a cerium-based nano material is characterized by comprising the following steps: the cerium-based nano material is prepared by a micro-channel reactor, and the micro-channel reactor at least comprises a section I, a section II, a section III and a section IV which are sequentially connected along the flow direction of a solution; the preparation method comprises the following steps:
(1) a precipitation step: respectively pumping the aqueous solution of soluble cerium salt and the alkaline aqueous solution into a section I of the microchannel reactor from an inlet of the section I for precipitation reaction, controlling the pumping speed of the solutions to ensure that the stroke time of the mixed solution of the aqueous solution of the soluble cerium salt and the alkaline aqueous solution in the section I is 5-35s, and controlling the reaction temperature in the section I to be 0-50 ℃;
(2) an oxidation step: pumping oxidant into the inlet of the second section of the microchannel reactor;
(3) a dispersing step: pumping a dispersant solution into an inlet of a section III of the microchannel reactor;
(4) oil dissolving step: pumping an oil phase solution of long-chain organic acid into an inlet of an IV section of the microchannel reactor for modification reaction, controlling the pumping speed of the oil phase solution to ensure that the stroke time of the mixed solution in the IV section is 15-55s, and controlling the reaction temperature in the IV section to be 50-90 ℃;
(5) collecting the reaction solution in the microchannel reactor, standing for 12-24h, and layering to obtain an oil phase which is the cerium-based nano material solution;
the water solution and the alkaline water solution of the soluble cerium salt in the step (1), the oxidant in the step (2), the dispersant in the step (3) and the oil phase solution of the long-chain organic acid in the step (4) are continuously pumped until the preparation process is finished;
and controlling the pumping speed of the solution in each step to ensure that the molar ratio of the soluble cerium salt to the dispersant pumped in unit time is 100: 5-80.
2. The method of claim 1, wherein: controlling the pumping speed of the solution in each step, so that the molar ratio of the soluble cerium salt, the oxidant, the dispersant and the long-chain organic acid pumped in unit time is 100: 45-55: 5-80: 35-80.
3. The method of claim 2, wherein: controlling the pumping speed of the solution in each step, so that the molar ratio of the soluble cerium salt, the oxidant, the dispersant and the long-chain organic acid pumped in unit time is 100: 50: 63: 70.
4. the production method according to any one of claims 1 to 3, characterized in that: the soluble cerium salt adopts cerium nitrate or cerium acetate; the alkaline aqueous solution adopts ammonia water or sodium hydroxide aqueous solution; the oxidant is hydrogen peroxide or hypochlorite; the dispersant is one or more of sodium dodecyl benzene sulfonate, acetic acid, polyethylene glycol with molecular weight of 800-2000 and ethanolamine; the long-chain organic acid adopts saturated fatty acid of C8-C18; the oil phase solution adopts a long-chain aliphatic hydrocarbon solvent D60 or D80.
5. The method of claim 4, wherein: the temperature in the section I in the step (1) is controlled to be 10-20 ℃; the temperature of the second section in the step (2) is controlled to be 25-35 ℃; the temperature of the section III in the step (3) is controlled to be 25-35 ℃; the temperature of the IV section in the step (4) is controlled to be 70-80 ℃.
6. The method of claim 5, wherein: controlling the pumping speed of the oxidant in the step (2) to ensure that the travel time of the mixed solution in the section II is 5-15 s; and (3) controlling the pumping speed of the dispersant solution in the step (3) to ensure that the travel time of the mixed solution in the section III is 5-15 s.
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