CN116899270A - Method for removing triurea from vehicle urea - Google Patents

Method for removing triurea from vehicle urea Download PDF

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CN116899270A
CN116899270A CN202311152495.5A CN202311152495A CN116899270A CN 116899270 A CN116899270 A CN 116899270A CN 202311152495 A CN202311152495 A CN 202311152495A CN 116899270 A CN116899270 A CN 116899270A
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molecular sieve
stirring
vehicle urea
triurea
deionized water
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CN116899270B (en
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胡坚南
张庆堂
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Shandong New Blue Environmental Protection Technology Co ltd
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D15/00Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08Selective adsorption, e.g. chromatography
    • B01D15/10Selective adsorption, e.g. chromatography characterised by constructional or operational features
    • B01D15/18Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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    • B01J20/106Perlite
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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    • B01J20/16Alumino-silicates
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract

The invention discloses a method for removing triurea from vehicle urea, which belongs to the technical field of vehicle urea, and comprises two steps of pretreatment and molecular sieve adsorption; the pretreatment, namely introducing the vehicle urea into a sealed reaction tank filled with ceramic filter materials, and adsorbing for 40-60min at normal temperature and normal pressure to obtain pretreated vehicle urea; the molecular sieve is used for adsorbing, the pretreated vehicle urea is introduced into a sealed reaction tank provided with a modified molecular sieve, and the vehicle urea is obtained after being adsorbed for 40-60min at normal temperature and normal pressure; the invention can remove the triurea in the vehicle urea, can remove other impurities, can not influence the concentration of the urea in the vehicle urea, and does not need cooling operation.

Description

Method for removing triurea from vehicle urea
Technical Field
The invention relates to the technical field of vehicle urea, in particular to a method for removing triurea from vehicle urea.
Background
The automobile urea is a pollutant harmful to the environment, can effectively decompose the generated nitrogen oxides into harmless nitrogen and water, and finally achieves the aim of safe emission, and the composition components of the automobile urea are 32.5 weight percent of high-purity urea and 67.5 weight percent of deionized water.
Impurities in the urea for the vehicle mainly comprise aldehydes, phosphates, metal ions, biuret and triurea, wherein the excessive content of the aldehydes and the phosphates can lead to the poisoning deactivation of a catalyst of a Selective Catalytic Reduction (SCR) system and the blockage of a nozzle, and then lead to crystallization; metal ions (calcium, iron, copper, zinc and the like) as impurities in the urea solution for the vehicle can influence the conversion efficiency of reduction in an SCR system and easily promote crystallization; too high biuret and tribiuret content can also induce crystallization; crystallization can cause vehicle operation problems, increasing the failure rate of the vehicle.
The raw materials of the vehicle urea are produced by coal or natural gas as raw materials, namely gas-head urea and coal-head urea, even though the production requirements of the vehicle urea raw materials are more strict than those of agricultural urea and industrial urea, the production process still has no way to completely avoid the generation of triurea, and urea molecules undergo condensation reaction to generate biuret and triurea due to the phenomenon of temperature rise in the process of producing the vehicle urea, and the triurea can generate cyanuric acid at high temperature to cause blockage and crystallization of the vehicle, so that the triurea is commonly existing in the vehicle urea, has serious influence on the operation of the vehicle, and is a technical problem which needs to be solved in the field of removing impurities of the vehicle urea.
At present, two most commonly used methods for removing urea biuret for vehicles exist, the first method is a method for reducing the temperature of the urea for vehicles and then performing ultrafiltration, but the method has high temperature reduction energy consumption and high equipment requirements, and other impurities in the urea for vehicles cannot be removed at the same time; the second method is to decompose and absorb the triurea by using an absorbent, but other impurities in the urea for the vehicle cannot be removed at the same time; the third method is to use molecular sieve to adsorb the triurea, but the molecular sieve is easy to absorb water, and the concentration of urea in the urea for vehicles is too high in the adsorption process.
Therefore, the method for removing the triurea from the vehicle urea is developed, the triurea in the vehicle urea can be removed, other impurities can be removed, the concentration of the urea in the vehicle urea is not influenced, and the cooling operation is not needed, so that the method is a technical problem which is urgently needed to be solved at present.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a method for removing the triurea in the vehicle urea, which can remove the triurea in the vehicle urea, can remove other impurities, can not influence the concentration of the urea in the vehicle urea, and does not need cooling operation.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for removing triurea from vehicle urea comprises two steps of pretreatment and molecular sieve adsorption;
the pretreatment step is that a sealed reaction tank filled with ceramic filter materials is introduced into the vehicle urea, and the pretreated vehicle urea is obtained after adsorption for 40-60min at normal temperature and normal pressure;
in the pretreatment step, the mass ratio of the urea for the vehicle to the ceramic filter material is 10:0.6-0.65;
the preparation method of the ceramic filter material comprises the steps of mixing dolomite powder, fly ash, clay, kaolin, pregelatinized starch, zeolite powder, ammonium carbonate, perlite powder and potassium feldspar powder, adding the mixture into a ball mill for ball milling, controlling the rotating speed during ball milling to be 300-400rpm, controlling the ball-material ratio to be 10-15:1, and obtaining mixed powder after ball milling is finished; uniformly mixing the mixed powder with water to obtain slurry; granulating the slurry to prepare particles with the granularity of 6-8 mm; drying the particles at 80-90 ℃ for 4-5h, drying at 120-130 ℃ for 5-6h, sintering at 700-800 ℃ for 1-1.5h, and sintering at 1100-1200 ℃ for 3-3.5h to obtain a primary ceramic filter material; soaking the primary ceramic filter material in the soaking solution completely, soaking at 15-35deg.C for 40-45min, and drying at 140-150deg.C for 50-60min to obtain soaked ceramic filter material; uniformly spraying the spray liquid on the surface of the soaked ceramic filter material, drying at 110-120 ℃ for 30-40min after spraying, and drying at 170-180 ℃ for 40-50min to obtain the ceramic filter material;
in the preparation of the ceramic filter material, the mass ratio of dolomite powder, fly ash, clay, kaolin, pregelatinized starch, zeolite powder, ammonium carbonate, perlite powder, potassium feldspar powder, water and spray liquid is 3-3.5:2.5-3:2-2.5:2-2.5:1-1.5:1-1.2:0.8-1:0.2-0.3:3.5-4:1-1.2;
the spraying speed of the spraying liquid is 0.05-0.06kg/min;
the preparation method of the soaking liquid comprises the steps of uniformly mixing high-hydrogen silicone oil, deionized water and absolute ethyl alcohol, adding sodium metaaluminate, stirring for 1.5-2 hours at the stirring speed of 100-200rpm at the temperature of 15-35 ℃, and then carrying out ultrasonic vibration for 20-30 minutes at the frequency of 20-30kHz to obtain the soaking liquid;
in the preparation of the soaking liquid, the mass ratio of the high hydrogen silicone oil to the deionized water to the absolute ethyl alcohol to the sodium metaaluminate is 1-1.2:3.2-3.5:8-8.5:0.04-0.05;
the hydrogen content of the high-hydrogen silicone oil is 1.56-1.6wt%;
the preparation method of the spray liquid comprises the steps of uniformly mixing tetraethoxysilane, gamma-aminopropyl triethoxysilane and methanol to obtain a methanol solution of the tetraethoxysilane; uniformly mixing ammonia water and methanol which are used for the first time to obtain an ammonia-methanol solution; uniformly mixing a methanol solution of tetraethoxysilane and an ammonia methanol solution, dropwise adding an aqueous hydrochloric acid solution while stirring at a stirring speed of 100-200rpm until the pH value is 5-5.5, stopping dropwise adding dopamine hydrochloride and L-lysine, stirring at a stirring speed of 100-200rpm at 35-45 ℃ for 2-2.5 hours, dropwise adding ammonia water used for the second time while stirring at a stirring speed of 100-200rpm until the pH value is 8-8.5, stopping dropwise adding, stirring at a stirring speed of 200-300rpm for 9-10 hours, adding n-hexane and silazane hexamethyldisilazane, stirring at a stirring speed of 40-60rpm at 70-75 ℃ for 9-10 hours, drying at 80-90 ℃ for 13-14 hours, and grinding to a particle size of 1-2 mu m to obtain gel powder; adding the gel powder into absolute ethyl alcohol, and performing ultrasonic oscillation at the frequency of 20-30kHz for 40-50min to obtain spray liquid;
in the preparation of the spray liquid, the mass ratio of tetraethoxysilane, gamma-aminopropyl triethoxysilane and methanol in the methanol solution of tetraethoxysilane is 1-1.1:0.02-0.025:2-2.2;
the mass ratio of the ammonia water to the methanol which are used for the first time in the ammonia methanol solution is 0.01-0.012:2-2.2;
the mass fraction of the ammonia water used for the first time is 25-28%;
the mass fraction of the hydrochloric acid aqueous solution is 1-1.2%;
the dropping speed of the hydrochloric acid aqueous solution is 0.02-0.025kg/mL;
the mass fraction of the ammonia water used for the second time is 25-28%;
the drop rate of the ammonia water used for the second time is 0.02-0.025kg/mL
The mass ratio of tetraethoxysilane in the methanol solution of tetraethoxysilane to ammonia water, dopamine hydrochloride, L-lysine, n-hexane, silazane hexamethyldisilazane and absolute ethyl alcohol which are used for the first time in the ammonia methanol solution is 1-1.1:0.01-0.012:0.004-0.005:0.002-0.003:10-11:1.2-1.5:9-10;
the molecular sieve adsorption step is that the pretreated vehicle urea is introduced into a sealed reaction tank with a modified molecular sieve, and is adsorbed for 40-60min at normal temperature and normal pressure to obtain the treated vehicle urea;
the mass ratio of the urea for the vehicle in the pretreatment step to the modified molecular sieve in the molecular sieve adsorption step is 10:0.6-0.65;
the preparation method of the modified molecular sieve comprises the steps of stirring a NaY molecular sieve, diamine hydrogen phosphate and deionized water which is used for the first time at 85-95 ℃ at a stirring speed of 100-200rpm for 15-20min, filtering, and drying filter residues at 110-120 ℃ for 1.5-2h to obtain a first-stage modified molecular sieve; stirring the primary modified molecular sieve, citric acid, phytic acid and deionized water used for the second time at 85-95 ℃ at a stirring speed of 100-200rpm for 1.5-2h, filtering, and drying filter residues at 110-120 ℃ for 1.5-2h to obtain a secondary modified molecular sieve; stirring the secondary modified molecular sieve, sodium hydroxide and deionized water used for the third time at 85-95 ℃ at a stirring speed of 100-200rpm for 1.5-2h, filtering, drying filter residues at 110-120 ℃ for 1.5-2h, and roasting at 900-950 ℃ for 1-1.5h to obtain the tertiary modified molecular sieve; uniformly spraying the casting solution on the surface of the three-stage modified molecular sieve, drying at 120-130 ℃ for 40-50min after spraying, and drying at 180-190 ℃ for 50-60min to obtain the modified molecular sieve;
in the preparation of the modified molecular sieve, the mass ratio of the NaY molecular sieve, the diamine hydrogen phosphate, the deionized water used for the first time, the citric acid, the phytic acid, the deionized water used for the second time, the sodium hydroxide, the deionized water used for the third time and the casting solution is 1-1.2:3.6-3.8:10-11:0.2-0.25:0.03-0.04:0.2-0.25:10-11:0.25-0.3;
the silicon-aluminum ratio of the NaY molecular sieve is 5-6, and the average grain size is 500-800nm;
the spraying speed of the casting film liquid is 0.04-0.05kg/min;
the preparation method of the casting film liquid comprises the steps of mixing 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonate, hydroxyethyl acrylate and deionized water used for the first time in a nitrogen atmosphere, stirring at a stirring speed of 100-120rpm for 30-40min at 30-40 ℃, adding potassium persulfate and sodium bisulfite, continuously stirring for 5-6h, filtering, cleaning filter residues for 3-4 times by using 2-3 times of deionized water, and drying at 120-130 ℃ to obtain betaine colloid nano particles; mixing betaine colloid nano particles, chitosan, glacial acetic acid, glutaraldehyde, nano zeolite powder and deionized water used for the second time, and stirring at 50-60 ℃ for 1.5-2 hours at a stirring speed of 100-120rpm to obtain a casting solution;
in the preparation of the casting film liquid, the mass ratio of 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonate, hydroxyethyl acrylate, deionized water used for the first time, potassium persulfate, sodium bisulphite, chitosan, glacial acetic acid, glutaraldehyde, nano zeolite powder and deionized water used for the second time is 0.3-0.32:0.1-0.11:2-2.5:0.012-0.015:0.012-0.015:1.8-2:1.5-2:0.6-0.7:0.04-0.05:200-220;
the particle size of the nano zeolite powder is 20-30nm.
Compared with the prior art, the invention has the beneficial effects that:
(1) The method for removing the triurea in the vehicle urea can remove the triurea in the vehicle urea, and reduce the content of the triurea in the vehicle urea to be undetected;
(2) The invention relates to a urea for vehiclesThe method for removing the triurea can remove other impurities, and the density (20 ℃) of the vehicle urea after removing the triurea is 1091.6-1092.2kg/m 3 Refractive index (20deg.C) 1.3829-1.3837, basicity (NH) 3 Calculated by HCHO) of 0.001-0.002wt%, aldehyde (calculated by HCHO) of 0.091-0.105mg/kg, phosphate (calculated by PO) 4 Calculated by weight) is 0.0027-0.0054mg/kg, and the content of biuret is undetected-0.0042% when aluminum, calcium, iron, chromium, potassium, magnesium, sodium, nickel, zinc, copper are all undetected;
(3) The method for removing the triurea from the vehicle urea does not influence the concentration of the urea in the vehicle urea;
(4) The method for removing the triurea from the vehicle urea does not need cooling operation, avoids high energy consumption and has low requirements on equipment;
(5) The method for removing the triurea from the vehicle urea can recycle the used ceramic filter material and the modified molecular sieve after treatment, and can reduce the treatment cost of the vehicle urea.
Detailed Description
Specific embodiments of the present invention will now be described in order to provide a clearer understanding of the technical features, objects and effects of the present invention.
Example 1
A method for removing triurea from vehicle urea specifically comprises the following steps:
1. pretreatment: introducing 10kg of vehicle urea into a sealed reaction tank filled with 0.6kg of ceramic filter material, and adsorbing for 40min at normal temperature and normal pressure to obtain pretreated vehicle urea;
the urea for the vehicle has the urea content of 32.3 weight percent and the density (20 ℃) of 1091.4kg/m 3 Refractive index (20 ℃ C.) of 1.3827, basicity (as NH) 3 Calculated as HCHO) of 0.087wt%, aldehyde content of 10.2mg/kg, phosphate (calculated as PO) 4 Calculated as) 2.4mg/kg, 2.1mg/kg of aluminum, 0.9mg/kg of calcium, 0.6mg/kg of iron, 0.5mg/kg of chromium, 1.0mg/kg of potassium, 0.3mg/kg of magnesium, 1.5mg/kg of sodium, 0.7mg/kg of nickel, 0.2mg/kg of zinc, 0.2mg/kg of copperkg, biuret content 2.4% and triurea content 1.2%;
the preparation method of the ceramic filter material comprises the following steps: mixing 3kg of dolomite powder, 2.5kg of fly ash, 2kg of clay, 2kg of kaolin, 2kg of pregelatinized starch, 1kg of zeolite powder, 1kg of ammonium carbonate, 0.8kg of perlite powder and 0.2kg of potassium feldspar powder, adding into a ball mill for ball milling, controlling the rotating speed during ball milling to 300rpm, controlling the ball-material ratio to be 10:1, and obtaining mixed powder after ball milling is finished; uniformly mixing the mixed powder with 3.5kg of water to obtain slurry; granulating the slurry to prepare particles with the granularity of 6 mm; drying the particles at 80 ℃ for 4 hours, drying the particles at 120 ℃ for 5 hours, sintering the particles at 700 ℃ for 1 hour, and sintering the particles at 1100 ℃ for 3 hours to obtain a primary ceramic filter material; completely soaking the primary ceramic filter material in the soaking solution, soaking at 15 ℃ for 40min, and drying at 140 ℃ for 50min to obtain a ceramic filter material after soaking treatment; uniformly spraying 1kg of spraying liquid on the surface of the soaked ceramic filter material, controlling the spraying speed to be 0.05kg/min, drying at 110 ℃ for 30min after spraying, and drying at 170 ℃ for 40min to obtain the ceramic filter material;
the preparation method of the soaking liquid comprises the following steps: uniformly mixing 1kg of high-hydrogen silicone oil, 3.2kg of deionized water and 8kg of absolute ethyl alcohol, adding 0.04kg of sodium metaaluminate, stirring at 15 ℃ for 1.5h at a stirring speed of 100rpm, and then carrying out ultrasonic vibration at a frequency of 20kHz for 20min to obtain a soaking solution;
the hydrogen content of the high-hydrogen silicone oil is 1.56wt%;
the preparation method of the spray liquid comprises the following steps: uniformly mixing 1kg of tetraethoxysilane, 0.02kg of gamma-aminopropyl triethoxysilane and 2kg of methanol to obtain a methanol solution of the tetraethoxysilane; uniformly mixing 0.01kg of ammonia water with the mass fraction of 25% and 2kg of methanol to obtain an ammonia methanol solution; uniformly mixing a methanol solution of tetraethoxysilane and an ammonia methanol solution, dropwise adding a hydrochloric acid aqueous solution with the mass fraction of 1% while stirring at the stirring speed of 100rpm, controlling the dropwise adding speed of the hydrochloric acid aqueous solution to be 0.02kg/mL, stopping dropwise adding until the pH value is 5, adding 0.004kg of dopamine hydrochloride and 0.002kg of L-lysine, stirring at the stirring speed of 100rpm at 35 ℃ for 2 hours, then dropwise adding ammonia water with the mass fraction of 25% while stirring at the stirring speed of 100rpm, controlling the dropwise adding speed of the ammonia water to be 0.02kg/mL until the pH value is 8, stirring at the stirring speed of 200rpm for 9 hours, adding 10kg of n-hexane and 1.2kg of silazane hexamethyldisilazane, stirring at the stirring speed of 40rpm at 70 ℃ for 9 hours, drying at 80 ℃ for 13 hours, and grinding to the particle size of 1 mu m to obtain gel powder; adding the gel powder into 9kg of absolute ethyl alcohol, and carrying out ultrasonic oscillation at the frequency of 20kHz for 40min to obtain spray liquid;
2. molecular sieve adsorption: introducing the pretreated vehicle urea into a sealed reaction tank filled with 0.6kg of modified molecular sieve, and adsorbing for 40min at normal temperature and normal pressure to obtain the treated vehicle urea;
the urea content in the treated vehicle urea is 32.3wt percent, and the density (20 ℃) is 1091.6kg/m 3 Refractive index (20 ℃ C.) of 1.3829, basicity (as NH) 3 Calculated as HCHO) of 0.002wt%, aldehyde content of 0.105mg/kg, phosphate (calculated as PO) 4 Calculated) 0.0054mg/kg, none of aluminium, calcium, iron, chromium, potassium, magnesium, sodium, nickel, zinc, copper, biuret content 0.0042%, none of biuret;
the preparation method of the modified molecular sieve comprises the following steps: stirring 1kg of NaY molecular sieve, 3.6kg of diamine hydrogen phosphate and 10kg of deionized water at 85 ℃ for 15-20min at a stirring speed of 100rpm, filtering, and drying the filter residue at 110 ℃ for 1.5h to obtain a first-stage modified molecular sieve; stirring the first-stage modified molecular sieve, 0.2kg of citric acid, 0.03kg of phytic acid and 10kg of deionized water at 85 ℃ at a stirring speed of 100rpm for 1.5 hours, filtering, and drying filter residues at 110 ℃ for 1.5 hours to obtain a second-stage modified molecular sieve; stirring the secondary modified molecular sieve, 0.2kg of sodium hydroxide and 10kg of deionized water at 85 ℃ at a stirring speed of 100rpm for 1.5 hours, filtering, drying filter residues at 110 ℃ for 1.5 hours, and roasting at 900 ℃ for 1 hour to obtain a tertiary modified molecular sieve; uniformly spraying 0.25kg of casting solution on the surface of the three-stage modified molecular sieve, controlling the spraying speed to be 0.04kg/min, drying at 120 ℃ for 40min after spraying, and drying at 180 ℃ for 50min to obtain the modified molecular sieve;
the silicon-aluminum ratio of the NaY molecular sieve is 5, and the average grain size is 500nm;
the preparation method of the casting film liquid comprises the following steps: mixing 0.3kg of 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonate, 0.1kg of hydroxyethyl acrylate and 2kg of deionized water in a nitrogen atmosphere, stirring at 30 ℃ for 30min at a stirring speed of 100rpm, adding 0.012kg of potassium persulfate and 0.012kg of sodium bisulfite, continuously stirring for 5h, filtering, cleaning filter residues with 2 times of deionized water for 3 times, and drying at 120 ℃ to obtain betaine colloid nano particles; mixing betaine colloid nano particles, 1.8kg of chitosan, 1.5kg of glacial acetic acid, 0.6kg of glutaraldehyde, 0.04kg of nano zeolite powder and 200kg of deionized water, and stirring at 50 ℃ for 1.5 hours at a stirring speed of 100rpm to obtain a casting solution;
the particle size of the nano zeolite powder is 20nm.
Example 2
A method for removing triurea from vehicle urea specifically comprises the following steps:
1. pretreatment: introducing 10kg of vehicle urea into a sealed reaction tank filled with 0.62kg of ceramic filter material, and adsorbing for 50min at normal temperature and normal pressure to obtain pretreated vehicle urea;
the urea for the vehicle has the urea content of 32.5 weight percent and the density (20 ℃) of 1091.7kg/m 3 Refractive index (20 ℃ C.) of 1.3829, basicity (as NH) 3 Calculated as HCHO) of 0.091wt%, aldehyde content of 10.4mg/kg, phosphate (calculated as PO) 4 Calculated) content of 2.5mg/kg, aluminum content of 2.2mg/kg, calcium content of 0.8mg/kg, iron content of 0.5mg/kg, chromium content of 0.7mg/kg, potassium content of 1.1mg/kg, magnesium content of 0.4mg/kg, sodium content of 1.3mg/kg, nickel content of 0.6mg/kg, zinc content of 0.2mg/kg, copper content of 0.3mg/kg, biuret content of 2.5% and triurea content of 1.1%;
the preparation method of the ceramic filter material comprises the following steps: mixing 3.2kg of dolomite powder, 2.8kg of fly ash, 2.5kg of clay, 2.2kg of kaolin, 2.2kg of pregelatinized starch, 1.2kg of zeolite powder, 1.1kg of ammonium carbonate, 0.9kg of perlite powder and 0.25kg of potassium feldspar powder, adding the mixture into a ball mill, performing ball milling, controlling the rotating speed during ball milling to be 350rpm, controlling the ball-to-material ratio to be 12:1, and obtaining mixed powder after the ball milling is finished; uniformly mixing the mixed powder with 3.8kg of water to obtain slurry; granulating the slurry to prepare particles with the granularity of 7 mm; drying the particles at 85 ℃ for 4.5 hours, drying the particles at 125 ℃ for 5.5 hours, sintering the particles at 750 ℃ for 1.2 hours, and sintering the particles at 1150 ℃ for 3.2 hours to obtain a primary ceramic filter material; completely soaking the primary ceramic filter material in the soaking solution, soaking at 25 ℃ for 42min, and drying at 145 ℃ for 55min to obtain a ceramic filter material after soaking treatment; uniformly spraying 1.1kg of spraying liquid on the surface of the ceramic filter material after the soaking treatment, controlling the spraying speed to be 0.05kg/min, drying at 115 ℃ for 35min after the spraying is finished, and drying at 175 ℃ for 45min to obtain the ceramic filter material;
the preparation method of the soaking liquid comprises the following steps: uniformly mixing 1.1kg of high-hydrogen silicone oil, 3.4kg of deionized water and 8.2kg of absolute ethyl alcohol, adding 0.04kg of sodium metaaluminate, stirring at 25 ℃ for 1.7h at a stirring speed of 150rpm, and then performing ultrasonic vibration at 25kHz for 25min to obtain a soaking solution;
the hydrogen content of the high-hydrogen silicone oil is 1.58wt%;
the preparation method of the spray liquid comprises the following steps: uniformly mixing 1.05kg of tetraethoxysilane, 0.022kg of gamma-aminopropyl triethoxysilane and 2.1kg of methanol to obtain a methanol solution of the tetraethoxysilane; uniformly mixing 0.011kg of ammonia water with the mass fraction of 26% and 2.1kg of methanol to obtain an ammonia methanol solution; uniformly mixing a methanol solution of tetraethoxysilane and an ammonia methanol solution, dropwise adding a hydrochloric acid aqueous solution with the mass fraction of 1.1% while stirring at a stirring speed of 150rpm, controlling the dropwise adding speed of the hydrochloric acid aqueous solution to be 0.022kg/mL until the pH value is 5.2, stopping dropwise adding, adding 0.005kg of dopamine hydrochloride and 0.002kg of L-lysine, stirring at a stirring speed of 150rpm for 2.2 hours at 40 ℃, then dropwise adding ammonia water with the mass fraction of 26% while stirring at a stirring speed of 150rpm, controlling the dropwise adding speed of the ammonia water to be 0.022kg/mL until the pH value is 8.2, stopping dropwise adding at a stirring speed of 250rpm for 9.5 hours, adding 10.5kg of n-hexane and 1.4kg of silazane hexamethyldisilazane, stirring at a stirring speed of 50rpm for 9.5 hours at 72 ℃, drying at 85 ℃ for 13.5 hours until the particle size is 2 mu m, and obtaining gel powder; adding the gel powder into 9.5kg of absolute ethyl alcohol, and carrying out ultrasonic oscillation at the frequency of 25kHz for 45min to obtain spray liquid;
2. molecular sieve adsorption: introducing the pretreated vehicle urea into a sealed reaction tank filled with 0.62kg of modified molecular sieve, and adsorbing for 50min at normal temperature and normal pressure to obtain the treated vehicle urea;
the urea content in the treated vehicle urea is 32.5wt percent, and the density (20 ℃) is 1091.8kg/m 3 Refractive index (20 ℃ C.) of 1.3831, basicity (as NH) 3 Calculated as HCHO) of 0.001wt%, aldehyde content of 0.091mg/kg, phosphate (calculated as PO) 4 Calculated) content of 0.0027mg/kg, aluminum, calcium, iron, chromium, potassium, magnesium, sodium, nickel, zinc, copper were not detected, biuret and tribiuret were not detected;
the preparation method of the modified molecular sieve comprises the following steps: stirring 1.1kg of NaY molecular sieve, 3.7kg of diamine hydrogen phosphate and 10.5kg of deionized water at 90 ℃ for 18min at a stirring speed of 150rpm, filtering, and drying the filter residue at 115 ℃ for 1.8h to obtain a first-stage modified molecular sieve; stirring the first-stage modified molecular sieve, 0.22kg of citric acid, 0.04kg of phytic acid and 10.5kg of deionized water at 90 ℃ at a stirring speed of 150rpm for 1.8 hours, filtering, and drying the filter residue at 115 ℃ for 1.8 hours to obtain a second-stage modified molecular sieve; stirring the secondary modified molecular sieve, 0.22kg of sodium hydroxide and 10.5kg of deionized water at 90 ℃ for 1.8 hours at a stirring speed of 150rpm, filtering, drying filter residues at 115 ℃ for 1.8 hours, and roasting at 920 ℃ for 1.2 hours to obtain a tertiary modified molecular sieve; uniformly spraying 0.28kg of casting solution on the surface of the three-stage modified molecular sieve, controlling the spraying speed to be 0.04kg/min, drying at 125 ℃ for 45min after spraying, and drying at 185 ℃ for 55min to obtain the modified molecular sieve;
the silicon-aluminum ratio of the NaY molecular sieve is 6, and the average grain size is 600nm;
the preparation method of the casting film liquid comprises the following steps: mixing 0.31kg of 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonate, 0.11kg of hydroxyethyl acrylate and 2.2kg of deionized water in a nitrogen atmosphere, stirring at a stirring speed of 110rpm at 35 ℃ for 35min, adding 0.014kg of potassium persulfate and 0.013kg of sodium bisulfite, continuing stirring for 5.5h, filtering, cleaning filter residues with 2 times of deionized water for 3 times, and drying at 125 ℃ to obtain betaine colloid nano particles; mixing betaine colloid nano particles, 1.9kg of chitosan, 1.7kg of glacial acetic acid, 0.65kg of glutaraldehyde, 0.04kg of nano zeolite powder and 210kg of deionized water, and stirring at a stirring speed of 110rpm at 55 ℃ for 1.7h to obtain a casting solution;
the particle size of the nano zeolite powder is 30nm.
Example 3
A method for removing triurea from vehicle urea specifically comprises the following steps:
1. pretreatment: introducing 10kg of vehicle urea into a sealed reaction tank filled with 0.65kg of ceramic filter material, and adsorbing for 60min at normal temperature and normal pressure to obtain pretreated vehicle urea;
the urea for the vehicle has the urea content of 32.7 weight percent and the density (20 ℃) of 1091.9kg/m 3 Refractive index (20 ℃ C.) of 1.3831, basicity (as NH) 3 Calculated as HCHO) of 0.093wt%, aldehyde content of 10.5mg/kg, phosphate (calculated as PO) 4 Calculated) content of 2.6mg/kg, aluminum content of 2.2mg/kg, calcium content of 0.8mg/kg, iron content of 0.6mg/kg, chromium content of 0.7mg/kg, potassium content of 1.1mg/kg, magnesium content of 0.3mg/kg, sodium content of 1.4mg/kg, nickel content of 0.6mg/kg, zinc content of 0.2mg/kg, copper content of 0.3mg/kg, biuret content of 2.7% and triurea content of 1.3%;
the preparation method of the ceramic filter material comprises the following steps: mixing 3.5kg of dolomite powder, 3kg of fly ash, 3kg of clay, 2.5kg of kaolin, 2.5kg of pregelatinized starch, 1.5kg of zeolite powder, 1.2kg of ammonium carbonate, 1kg of perlite powder and 0.3kg of potassium feldspar powder, adding the mixture into a ball mill for ball milling, controlling the rotation speed during ball milling to 400rpm, controlling the ball-to-material ratio to 15:1 and the time to 50min, and obtaining mixed powder after the ball milling is finished; uniformly mixing the mixed powder with 4kg of water to obtain slurry; granulating the slurry to prepare particles with the granularity of 8 mm; drying the particles at 90 ℃ for 5 hours, drying the particles at 130 ℃ for 6 hours, sintering the particles at 800 ℃ for 1.5 hours, and sintering the particles at 1200 ℃ for 3.5 hours to obtain a primary ceramic filter material; completely soaking the primary ceramic filter material in the soaking solution, soaking at 35 ℃ for 45min, and drying at 150 ℃ for 60min to obtain a ceramic filter material after soaking treatment; uniformly spraying 1.2kg of spraying liquid on the surface of the soaked ceramic filter material, controlling the spraying speed to be 0.06kg/min, drying at 120 ℃ for 40min after spraying, and drying at 180 ℃ for 50min to obtain the ceramic filter material;
the preparation method of the soaking liquid comprises the following steps: uniformly mixing 1.2kg of high-hydrogen silicone oil, 3.5kg of deionized water and 8.5kg of absolute ethyl alcohol, adding 0.05kg of sodium metaaluminate, stirring at 35 ℃ for 2 hours at a stirring speed of 200rpm, and then performing ultrasonic vibration at a frequency of 30kHz for 30 minutes to obtain a soaking solution;
the hydrogen content of the high-hydrogen silicone oil is 1.6wt%;
the preparation method of the spray liquid comprises the following steps: uniformly mixing 1.1kg of tetraethoxysilane, 0.025kg of gamma-aminopropyl triethoxysilane and 2.2kg of methanol to obtain a methanol solution of the tetraethoxysilane; uniformly mixing 0.012kg of 28% ammonia water and 2.2kg of methanol to obtain an ammonia methanol solution; uniformly mixing a methanol solution of tetraethoxysilane and an ammonia methanol solution, dropwise adding a hydrochloric acid aqueous solution with the mass fraction of 1.2% while stirring at the stirring speed of 200rpm, controlling the dropwise adding speed of the hydrochloric acid aqueous solution to be 0.025kg/mL until the pH value is 5.5, stopping dropwise adding, adding 0.005kg of dopamine hydrochloride and 0.003kg of L-lysine, stirring at the stirring speed of 200rpm for 2.5 hours at 45 ℃, then dropwise adding ammonia water with the mass fraction of 28% while stirring at the stirring speed of 200rpm, controlling the dropwise adding speed of the ammonia water to be 0.025kg/mL until the pH value is 8.5, stopping dropwise adding at the stirring speed of 300rpm for 10 hours, adding 11kg of n-hexane and 1.5kg of silazane hexamethyldisilazane, stirring at the stirring speed of 60rpm for 10 hours at 75 ℃, drying at 90 ℃ for 14 hours, and grinding to the particle size of 2 mu m to obtain gel powder; adding the gel powder into 10kg of absolute ethyl alcohol, and carrying out ultrasonic oscillation at the frequency of 30kHz for 50min to obtain spray liquid;
2. molecular sieve adsorption: introducing the pretreated vehicle urea into a sealed reaction tank filled with 0.65kg of modified molecular sieve, and adsorbing for 60min at normal temperature and normal pressure to obtain the treated vehicle urea;
the urea content in the treated vehicle urea is 32.7wt percent, and the density (20 ℃) is 1092.2kg/m 3 Refractive index (20 ℃ C.) of 1.3837, basicity (as NH) 3 Calculated as HCHO) of 0.002wt% and aldehydes (calculated as HCHO)) The content was 0.098mg/kg, phosphate (as PO 4 Calculated) 0.0046mg/kg, aluminum, calcium, iron, chromium, potassium, magnesium, sodium, nickel, zinc, copper were all undetected, biuret content was 0.0019%, and triurea was not detected;
the preparation method of the modified molecular sieve comprises the following steps: stirring 1.2kg of NaY molecular sieve, 3.8kg of diamine hydrogen phosphate and 11kg of deionized water at 95 ℃ for 20min at a stirring speed of 200rpm, filtering, and drying the filter residue at 120 ℃ for 2h to obtain a first-stage modified molecular sieve; stirring the first-stage modified molecular sieve, 0.25kg of citric acid, 0.04kg of phytic acid and 11kg of deionized water at 95 ℃ for 2 hours at a stirring speed of 200rpm, filtering, and drying filter residues at 120 ℃ for 2 hours to obtain a second-stage modified molecular sieve; stirring the secondary modified molecular sieve, 0.25kg of sodium hydroxide and 11kg of deionized water at 95 ℃ for 2 hours at a stirring speed of 200rpm, filtering, drying filter residues at 120 ℃ for 2 hours, and roasting at 950 ℃ for 1.5 hours to obtain a tertiary modified molecular sieve; uniformly spraying 0.3kg of casting solution on the surface of the three-stage modified molecular sieve, controlling the spraying speed to be 0.05kg/min, drying at 130 ℃ for 50min after spraying, and drying at 190 ℃ for 60min to obtain the modified molecular sieve;
the silicon-aluminum ratio of the NaY molecular sieve is 6, and the average grain size is 800nm;
the preparation method of the casting film liquid comprises the following steps: mixing 0.32kg of 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonate, 0.11kg of hydroxyethyl acrylate and 2.5kg of deionized water in a nitrogen atmosphere, stirring at a stirring speed of 120rpm at 40 ℃ for 40min, adding 0.015kg of potassium persulfate and 0.015kg of sodium bisulfite, continuously stirring for 6h, filtering, cleaning filter residues with 3 times of deionized water for 4 times, and drying at 130 ℃ to obtain betaine colloid nano particles; mixing betaine colloid nano particles, 2kg of chitosan, 2kg of glacial acetic acid, 0.7kg of glutaraldehyde, 0.05kg of nano zeolite powder and 220kg of deionized water, and stirring at 60 ℃ for 2 hours at a stirring speed of 120rpm to obtain a casting solution;
the particle size of the nano zeolite powder is 30nm.
Comparative example 1
The method for removing the triurea from the urea for the vehicle described in example 2 is different in that: in the step 1, the step of soaking the primary ceramic filter material in the soaking liquid is omitted in the preparation of the ceramic filter material, namely, the preparation method of the ceramic filter material is changed into the following steps:
uniformly mixing 3.2kg of dolomite powder, 2.8kg of fly ash, 2.5kg of clay, 2.2kg of kaolin, 2.2kg of pregelatinized starch, 1.2kg of zeolite powder, 1.1kg of ammonium carbonate, 0.9kg of perlite powder and 0.25kg of potassium feldspar powder, adding the mixture into a ball mill for ball milling, controlling the rotating speed during ball milling to be 350rpm, controlling the ball-to-material ratio to be 12:1, and obtaining mixed powder after ball milling is finished; uniformly mixing the mixed powder with 3.8kg of water to obtain slurry; granulating the slurry to prepare particles with the granularity of 7 mm; drying the particles at 85 ℃ for 4.5 hours, drying the particles at 125 ℃ for 5.5 hours, sintering the particles at 750 ℃ for 1.2 hours, and sintering the particles at 1150 ℃ for 3.2 hours to obtain a primary ceramic filter material; uniformly spraying 1.1kg of spray liquid on the surface of the primary ceramic filter material, controlling the spraying speed to be 0.05kg/min, drying at 115 ℃ for 35min after spraying, and drying at 175 ℃ for 45min to obtain the ceramic filter material;
the spray liquid was prepared in the same manner as in example 2;
in the step 2, in the preparation of the modified molecular sieve, the first-stage modification, the second-stage modification and the third-stage modification of the NaY molecular sieve are omitted, namely, the preparation method of the modified molecular sieve is changed into:
uniformly spraying 0.28kg of casting solution on the surface of 1.1kg of NaY molecular sieve, controlling the spraying speed to be 0.04kg/min, drying at 125 ℃ for 45min after spraying, and drying at 185 ℃ for 55min to obtain the modified molecular sieve;
the preparation method of the casting solution is the same as that of the example 2;
the urea content in the treated vehicle urea obtained in the 2 nd molecular sieve adsorption step is 36.7wt% and the density (20 ℃) is 1132.4kg/m 3 Refractive index (20 ℃ C.) of 1.3948, basicity (as NH) 3 Calculated as HCHO) of 0.002wt%, aldehyde content of 0.096mg/kg, phosphate (calculated as PO) 4 Calculated as 0.0035mg/kg, aluminum, calcium, iron, chromium, potassium, magnesium, sodium, nickel, zinc, copper were not detected, biuret content was 0.01%, and triurea was not detected。
Comparative example 2
The method for removing the triurea from the urea for the vehicle described in example 2 is different in that: in the step 1, the step of uniformly spraying spray liquid on the surface of the soaked ceramic filter material is omitted in the preparation of the ceramic filter material, namely, the soaked ceramic filter material is used as the ceramic filter material to pretreat the vehicle urea;
the urea content in the treated vehicle urea obtained in the 2 nd molecular sieve adsorption step is 33.1wt%, and the density (20 ℃) is 1097.8kg/m 3 Refractive index (20 ℃ C.) of 1.3873, basicity (as NH) 3 Calculated as HCHO) of 0.019wt%, aldehyde content of 2.571mg/kg, phosphate (calculated as PO) 4 Calculated) is 0.2874mg/kg, the aluminum is 0.07mg/kg, the calcium is 0.05mg/kg, the potassium is 0.05mg/kg, the sodium is 0.1mg/kg, none of iron, chromium, magnesium, nickel, zinc and copper is detected, the biuret is 0.13% and the triurea is 0.07%.
Comparative example 3
The method for removing the triurea from the urea for the vehicle described in example 2 is different in that: in the step 2, in the preparation of the modified molecular sieve, the step of uniformly spraying the casting solution on the surface of the three-stage modified molecular sieve is omitted, namely the three-stage modified molecular sieve is used as the modified molecular sieve to carry out molecular sieve adsorption on the pretreated vehicle urea;
the urea content in the treated vehicle urea obtained in the 2 nd molecular sieve adsorption step is 32.8wt%, and the density (20 ℃) is 1096.1kg/m 3 Refractive index (20 ℃ C.) of 1.3858, basicity (as NH) 3 Calculated as HCHO) of 0.008wt%, aldehyde content of 1.154mg/kg, phosphate (calculated as PO) 4 Calculated) is 0.0758mg/kg, the aluminum is 0.31mg/kg, the calcium is 0.12mg/kg, the iron is 0.11mg/kg, the chromium is 0.08mg/kg, the potassium is 0.10mg/kg, the sodium is 0.14mg/kg, the magnesium, nickel, zinc and copper are all undetected, the biuret is 0.08%, and the tribiuret is not detected.
As can be seen from the urea content in the urea for vehicles treated in examples 1-3 and comparative examples 1-2, the method of examples 1-3 can remove the triurea in the urea for vehicles, can remove other impurities, and also has no influence on the concentration of urea in the urea for vehicles, and comparative example 1 has a larger influence on the concentration of urea in the urea for vehicles, and comparative examples 2 and 3 have lower impurity removal capacity than examples 1-3;
through further analysis, the hydrophobicity of the primary ceramic filter material can be improved by fully soaking the primary ceramic filter material in the soaking liquid for soaking treatment, the adsorption of the primary ceramic filter material to water is avoided, and the hydrophobicity of the molecular sieve can be improved by carrying out primary modification, secondary modification and tertiary modification on the NaY molecular sieve, so that the adsorption of the NaY molecular sieve to water is avoided, and the influence on the concentration of urea in the urea for vehicles is avoided;
the spray liquid is uniformly sprayed on the surface of the soaked ceramic filter material, so that the adsorption capacity of the ceramic filter material can be improved; the film casting liquid is uniformly sprayed on the surface of the three-stage modified molecular sieve, so that the adsorption capacity of the modified molecular sieve can be improved; the ceramic filter material and the modified molecular sieve can carry out two-layer adsorption on impurities in the vehicle urea, so that the impurity content in the vehicle urea is reduced as much as possible.
The percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (9)

1. A method for removing triurea from vehicle urea is characterized by comprising two steps of pretreatment and molecular sieve adsorption;
the pretreatment step is that the vehicle urea is introduced into a sealed reaction tank filled with ceramic filter materials, and is adsorbed for 40-60min at normal temperature and normal pressure, so as to obtain pretreated vehicle urea;
the preparation method of the ceramic filter material comprises the steps of mixing dolomite powder, fly ash, clay, kaolin, pregelatinized starch, zeolite powder, ammonium carbonate, perlite powder and potassium feldspar powder, and then adding the mixture into a ball mill for ball milling to obtain mixed powder; uniformly mixing the mixed powder with water to obtain slurry; granulating the slurry to obtain granules; drying and sintering the particles to obtain a primary ceramic filter material; completely soaking the primary ceramic filter material in the soaking solution, and drying to obtain a ceramic filter material after soaking treatment; uniformly spraying spray liquid on the surface of the soaked ceramic filter material, and drying after spraying to obtain the ceramic filter material;
the preparation method of the soaking liquid comprises the steps of uniformly mixing high-hydrogen silicone oil, deionized water and absolute ethyl alcohol, adding sodium metaaluminate, stirring and carrying out ultrasonic vibration to obtain the soaking liquid;
the preparation method of the spray liquid comprises the steps of uniformly mixing tetraethoxysilane, gamma-aminopropyl triethoxysilane and methanol to obtain a methanol solution of the tetraethoxysilane; uniformly mixing ammonia water and methanol which are used for the first time to obtain an ammonia-methanol solution; uniformly mixing a methanol solution of tetraethoxysilane and an ammonia methanol solution, dropwise adding an aqueous solution of hydrochloric acid while stirring, stopping dropwise adding when the pH is regulated to 5-5.5, adding dopamine hydrochloride and L-lysine, stirring at 35-45 ℃, then dropwise adding ammonia water for secondary use while stirring, stopping dropwise adding when the pH is 8-8.5, continuing stirring, adding n-hexane and silazane hexamethyldisilazane, stirring at 70-75 ℃, drying and grinding to obtain gel powder; adding the gel powder into absolute ethyl alcohol, and carrying out ultrasonic oscillation to obtain a spray liquid;
the molecular sieve adsorption step is that the pretreated vehicle urea is introduced into a sealed reaction tank with a modified molecular sieve, and is adsorbed for 40-60min at normal temperature and normal pressure to obtain the treated vehicle urea;
the preparation method of the modified molecular sieve comprises the following steps: stirring a NaY molecular sieve, diamine hydrogen phosphate and deionized water used for the first time at 85-95 ℃, filtering, and drying filter residues to obtain a first-stage modified molecular sieve; stirring the first-stage modified molecular sieve, citric acid, phytic acid and deionized water used for the second time at 85-95 ℃, filtering, and drying filter residues to obtain a second-stage modified molecular sieve; stirring the secondary modified molecular sieve, sodium hydroxide and deionized water used for the third time at 85-95 ℃, filtering, drying and roasting filter residues to obtain a tertiary modified molecular sieve; uniformly spraying a casting solution on the surface of the three-stage modified molecular sieve, and drying after spraying to obtain the modified molecular sieve;
the preparation method of the casting film liquid comprises the following steps: mixing 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonate, hydroxyethyl acrylate and deionized water used for the first time in nitrogen atmosphere, stirring at 30-40 ℃, adding potassium persulfate and sodium bisulfite, continuously stirring, filtering, cleaning and drying filter residues to obtain betaine colloid nano particles; mixing betaine colloid nano particles, chitosan, glacial acetic acid, glutaraldehyde, nano zeolite powder and deionized water for the second time, and stirring at 50-60 ℃ to obtain a casting solution.
2. The method for removing triurea from vehicle urea according to claim 1, wherein in the pretreatment step, the mass ratio of the vehicle urea to the ceramic filter material is 10:0.6-0.65.
3. The method for removing triurea from vehicle urea according to claim 1, wherein in the preparation of the ceramic filter material, the mass ratio of dolomite powder, fly ash, clay, kaolin, pregelatinized starch, zeolite powder, ammonium carbonate, perlite powder, potassium feldspar powder, water and spray liquid is 3-3.5:2.5-3:2-2.5:2-2.5:1-1.5:1-1.2:0.8-1:0.2-0.3:3.5-4:1-1.2;
the spraying speed of the spraying liquid is 0.05-0.06kg/min.
4. The method for removing triurea from vehicle urea according to claim 1, wherein the mass ratio of high hydrogen silicone oil, deionized water, absolute ethyl alcohol and sodium metaaluminate in the preparation of the soaking solution is 1-1.2:3.2-3.5:8-8.5:0.04-0.05;
the hydrogen content of the high-hydrogen silicone oil is 1.56-1.6wt%.
5. The method for removing triurea from vehicle urea according to claim 1, wherein in the preparation of the spray liquid, the mass ratio of tetraethoxysilane, gamma-aminopropyl triethoxysilane and methanol in the methanol solution of tetraethoxysilane is 1-1.1:0.02-0.025:2-2.2;
the mass ratio of the ammonia water to the methanol which are used for the first time in the ammonia methanol solution is 0.01-0.012:2-2.2;
the mass ratio of tetraethoxysilane in the methanol solution of tetraethoxysilane to ammonia water, dopamine hydrochloride, L-lysine, n-hexane, silazane hexamethyldisilazane and absolute ethyl alcohol which are used for the first time in the ammonia methanol solution is 1-1.1:0.01-0.012:0.004-0.005:0.002-0.003:10-11:1.2-1.5:9-10.
6. The method for removing triurea from vehicle urea according to claim 1, wherein in the preparation of the spray liquid, the mass fraction of the ammonia water used for the first time is 25-28%;
the mass fraction of the hydrochloric acid aqueous solution is 1-1.2%;
the dropping speed of the hydrochloric acid aqueous solution is 0.02-0.025kg/mL;
the mass fraction of the ammonia water used for the second time is 25-28%;
the dropping speed of the ammonia water used for the second time is 0.02-0.025kg/mL.
7. The method for removing triurea from vehicle urea according to claim 1, wherein the mass ratio of the vehicle urea in the pretreatment step to the modified molecular sieve in the molecular sieve adsorption step is 10:0.6-0.65.
8. The method for removing triurea from vehicle urea according to claim 1, wherein in the preparation of the modified molecular sieve, the mass ratio of NaY molecular sieve, diamine hydrogen phosphate, deionized water used for the first time, citric acid, phytic acid, deionized water used for the second time, sodium hydroxide, deionized water used for the third time and casting solution is 1-1.2:3.6-3.8:10-11:0.2-0.25:0.03-0.04:10-11:0.2-0.25:10-11:0.25-0.3;
the silicon-aluminum ratio of the NaY molecular sieve is 5-6, and the average grain size is 500-800nm;
the spraying speed of the casting film liquid is 0.04-0.05kg/min.
9. The method for removing triurea from vehicle urea according to claim 1, wherein in the preparation of the casting solution, the mass ratio of 3- [ N, N-dimethyl- [2- (2-methylprop-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonate, hydroxyethyl acrylate, deionized water used for the first time, potassium persulfate, sodium bisulphite, chitosan, glacial acetic acid, glutaraldehyde, nanozeolite powder and deionized water used for the second time is 0.3-0.32:0.1-0.11:2-2.5:0.012-0.015:0.012-0.015:1.8-2:1.5-0.6-0.7:0.04-0.05:200-220;
the particle size of the nano zeolite powder is 20-30nm.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4677135A (en) * 1985-08-06 1987-06-30 Research Development Corp. Of Japan Method of preparing urea adsorbent
US20090057230A1 (en) * 2007-08-29 2009-03-05 Colonial Chemical Company Method and system for removing inpurities from a urea solution
CN105797584A (en) * 2016-03-29 2016-07-27 河北鑫达润滑油科技有限公司 Production method of vehicle-used urea solution
CN105854603A (en) * 2016-05-10 2016-08-17 南宁市夏阳化工科技有限责任公司 Diesel tail gas treating agent production method
CN106064020A (en) * 2016-06-28 2016-11-02 许江煌 A kind of preparation method of urea for vehicle
CN207042012U (en) * 2017-06-13 2018-02-27 山东新蓝环保科技有限公司 A kind of filter for urea liquid

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4677135A (en) * 1985-08-06 1987-06-30 Research Development Corp. Of Japan Method of preparing urea adsorbent
US20090057230A1 (en) * 2007-08-29 2009-03-05 Colonial Chemical Company Method and system for removing inpurities from a urea solution
CN105797584A (en) * 2016-03-29 2016-07-27 河北鑫达润滑油科技有限公司 Production method of vehicle-used urea solution
CN105854603A (en) * 2016-05-10 2016-08-17 南宁市夏阳化工科技有限责任公司 Diesel tail gas treating agent production method
CN106064020A (en) * 2016-06-28 2016-11-02 许江煌 A kind of preparation method of urea for vehicle
CN207042012U (en) * 2017-06-13 2018-02-27 山东新蓝环保科技有限公司 A kind of filter for urea liquid

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