CN117417273A - Preparation method of urea solution for vehicles - Google Patents
Preparation method of urea solution for vehicles Download PDFInfo
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- CN117417273A CN117417273A CN202311351377.7A CN202311351377A CN117417273A CN 117417273 A CN117417273 A CN 117417273A CN 202311351377 A CN202311351377 A CN 202311351377A CN 117417273 A CN117417273 A CN 117417273A
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- urea solution
- stirring
- impurity removing
- urea
- removing component
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000004202 carbamide Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 34
- 239000012535 impurity Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 14
- 239000012498 ultrapure water Substances 0.000 claims abstract description 14
- 239000012043 crude product Substances 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 10
- 230000009471 action Effects 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 8
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 7
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- 239000005642 Oleic acid Substances 0.000 claims description 7
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 7
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 7
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 7
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003480 eluent Substances 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- 238000011010 flushing procedure Methods 0.000 claims description 4
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 239000011247 coating layer Substances 0.000 claims description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 229920000877 Melamine resin Polymers 0.000 abstract description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 abstract description 2
- 239000013049 sediment Substances 0.000 abstract description 2
- 239000008187 granular material Substances 0.000 abstract 1
- 239000002198 insoluble material Substances 0.000 abstract 1
- 230000002265 prevention Effects 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 150000004753 Schiff bases Chemical group 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000007885 magnetic separation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/02—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds
- C07C273/14—Separation; Purification; Stabilisation; Use of additives
- C07C273/16—Separation; Purification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2067—Urea
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method of a vehicle urea solution, which belongs to the technical field of vehicle tail gas treatment and comprises the following steps: urea particles and ultrapure water are mixed according to the mass ratio of 32-35:65-68, stirring and mixing for 20-30min at 25-35 ℃ to obtain crude product, then adding magnetic impurity removing component, continuously stirring for 5-10min, separating magnetic impurity removing component by external magnetic field to obtain the urea solution for vehicle, the dosage of magnetic impurity removing component is 1-2% of that of crude product, after urea granules and ultrapure water are mixed, the magnetic impurity removing component is adopted to make adsorption impurity removing, so that biuret, metal ion and insoluble material in the urea solution for vehicle can be effectively and pertinently adsorbed, and the adsorption efficiency is high, and the urea solution for vehicle can be easily separated, and can obtain high-purity urea solution for vehicle, and can raise NH 3 Conversion efficiency, effective prevention of biuretProducts of melamine and other sediments, and the blockage of the SCR system is avoided.
Description
Technical Field
The invention belongs to the technical field of vehicle tail gas treatment, and particularly relates to a preparation method of a vehicle urea solution.
Background
Aiming at the problem of high PM and NOx in the exhaust gas of diesel vehicles, the existing mature exhaust gas treatment technology is to additionally arrange a set of post-treatment system at the exhaust hole of an engine, wherein the main pollutants in the exhaust gas are HC, CO, PM, NO x Etc., the technical routes adopted for treating these pollutants are also different, and NO is treated x Selective Catalytic Reduction (SCR) is used, which is located in the aftertreatment systemAt the end of the system, urea solution is mainly utilized to decompose and generate NH at high temperature 3 ，NH 3 NO in the tail gas x React to form harmless H 2 O and N 2 。
The existing urea for vehicles refers to urea aqueous solution, the main raw materials of which are urea crystals and ultrapure water, and also contain various impurities, mainly aldehydes, biuret, insoluble substances, phosphate, metal ions and the like, wherein the aldehydes and the biuret mainly originate from the urea crystals, the aldehydes and the biuret mainly influence the catalyst coating, influence the activity of the catalyst, and further influence NO x The conversion rate of the catalyst is particularly that aldehydes substances and biuret are subjected to polymerization reaction to generate high molecular compounds which are easily accumulated in a pipeline and a catalyst framework to cause pipeline blockage, insoluble substances are impurities insoluble in water in urea solution, the main hazard is represented by blockage of urea nozzles and pipelines, the influence of phosphate on an SCR system is mainly represented by passivation effect on a system catalyst, the activity of the catalyst is reduced, metal ions can cause the catalyst poisoning of the SCR system to cause the catalyst to lose activity, and the NO is seriously influenced x Conversion, it is therefore necessary to provide a high purity urea solution for vehicles.
Disclosure of Invention
The invention aims to provide a preparation method of a vehicle urea solution, which is characterized in that the self-made magnetic impurity removal component is used for treating the vehicle urea solution to effectively remove impurities in the urea solution, obviously reduce the content of biuret and solve the problems of low purity and NO of the existing vehicle urea x The conversion rate is not high.
The aim of the invention can be achieved by the following technical scheme:
the preparation method of the urea solution for the vehicle comprises the following steps:
urea particles and ultrapure water are mixed according to the mass ratio of 32-35: adding 65-68 into a stirring tank, stirring and mixing at 25-35deg.C and 200-300r/min for 20-30min to obtain crude product, adding magnetic impurity removing component, stirring for 5-10min, and separating magnetic impurity removing component by external magnetic field to obtain the urea solution for vehicle.
Further, the dosage of the magnetic impurity removing component is 1-2% of the mass of the crude product.
Further, the magnetic impurity removing component is specifically prepared by the following steps:
uniformly mixing biuret, methanol and deionized water, adding methacrylic acid, stirring for 10-30min, adding functional monomer, glycol dimethacrylate and surface modified magnetic carrier, ultrasonically mixing for 30min to obtain mixed solution a, adding polyvinylpyrrolidone and absolute ethyl alcohol into a reaction kettle, heating to 60 ℃ under the protection of nitrogen, adding the mixed solution a and azodiisobutyronitrile, carrying out heat preservation and stirring for reaction for 24h, cooling to room temperature after the reaction is finished, separating products under the action of an external magnetic field, and respectively using distilled water, methanol and acetic acid according to the volume ratio of 8:2, flushing the mixed solution until the eluent is detected by liquid chromatography-mass spectrometry to have no biuret, and finally drying at 60 ℃ to obtain a magnetic impurity-removing component;
wherein, the dosage ratio of biuret, methanol, deionized water, functional monomer, methacrylic acid, ethylene glycol dimethacrylate, surface modified magnetic carrier, polyvinylpyrrolidone, absolute ethanol and azodiisobutyronitrile is 0.1g:10mL:10mL:0.3-0.5g:0.4-0.6g:2.8-3.4g:0.9-1.3g:0.4g:100mL:0.1g, first mix biuret and methacrylic acid, form monomer-template molecule complex through hydrogen bond, then under the action of initiator, make monomer-template molecule complex, functional monomer, glycol dimethacrylate and surface modification magnetic carrier polymerize, form hybrid, finally elute the biuret template molecule from hybrid, form the cavity identical with biuret molecule shape, size and specific recognition in hybrid, add it into car urea solution, the dispersibility is high, the suspension is good, can carry on specific recognition, absorption to biuret, and separate with car urea solution under the action of external magnetic field, easy to operate and separation time is short, have the characteristics such as being strong in interference resistance, high in selectivity, stability are good, long service life, in addition, it contains Schiff base structure and phenolic hydroxyl, have better complexation with metal ion, can reduce the content of metal ion in car urea solution, contain carboxyl, phenolic hydroxyl and high molecular weight long polymer chain, can be through static absorption and other effects with car urea solution, can further improve the purity of car urea.
Further, the surface-modified magnetic carrier is produced by the steps of:
mixing a magnetic carrier with distilled water, adding oleic acid under nitrogen protection at 80 ℃, stirring for 30min, cooling to 50 ℃, adding polyethylene glycol, performing suction filtration after ultrasonic treatment for 15min, washing a filter cake, and drying to obtain a surface modified magnetic carrier, wherein the dosage ratio of the magnetic carrier, distilled water, oleic acid and polyethylene glycol is 2g:40mL:2mL:2.5-3.4g, wherein the molecular weight of polyethylene glycol is 6000, oleic acid and polyethylene glycol are adopted to coat the magnetic carrier, and the hydrophobic end of the polyethylene glycol and the hydrophobic end of the oleic acid form double-layer micelle, so that the dispersibility and suspension property of the magnetic carrier in the solution are improved.
Further, the magnetic carrier is nano ferroferric oxide with a silicon dioxide coating layer loaded on the surface, and the magnetic carrier is specifically prepared by the following steps:
fe is added to 3 O 4 Ultrasonic mixing nanoparticle and ethanol solution for 10min, adding ammonia water, stirring for 10min, dripping ethyl orthosilicate, reacting at 45deg.C for 12 hr under stirring at 400-500r/min, magnetic separating, collecting, alternately washing with anhydrous ethanol and deionized water for 3 times, and lyophilizing to obtain magnetic carrier, fe 3 O 4 The dosage ratio of the nano particles, the ethanol solution, the ammonia water and the tetraethoxysilane is 0.2g:200mL:5mL:1.5mL, the volume fraction of the ethanol solution is 80%, and the mass fraction of the ammonia water is 28%.
Further, the functional monomer is prepared by the following steps:
adding acrylamide, o-hydroxybenzaldehyde and absolute ethyl alcohol into a flask, heating to reflux reaction for 10-12h, and removing the absolute ethyl alcohol by rotary evaporation after the reaction is finished, wherein the molar ratio of the acrylamide to the o-hydroxybenzaldehyde is 1-1.1:1, taking acrylamide and o-hydroxybenzaldehyde as raw materials, and obtaining a functional monomer through Schiff base reaction.
Furthermore, the ultrapure water is required to meet the technical requirements for the ultrapure water in GB29518-2013 (AUS 32) standard of a nitrogen oxide reducing agent urea aqueous solution for a diesel engine.
The invention has the beneficial effects that:
the invention provides a preparation method of a vehicular urea solution, which comprises the steps of mixing urea particles with ultrapure water, and then adopting a magnetic impurity removal component to adsorb and remove impurities, so that biuret, metal ions, insoluble matters and the like in the vehicular urea solution can be effectively and pertinently adsorbed, the adsorption efficiency is high, the separation is easy, the vehicular urea solution with high purity can be obtained, and the NH is improved 3 The conversion efficiency is improved, products of sediments such as biuret, melamine and the like are effectively prevented, and the blockage of an SCR system is avoided.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. 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
The magnetic impurity removing component is prepared by the following steps:
uniformly mixing 0.1g of biuret, 10mL of methanol and 10mL of deionized water, adding 0.4g of methacrylic acid, stirring for 10min, adding 0.3g of functional monomer, 2.8g of ethylene glycol dimethacrylate and 0.9g of surface modification magnetic carrier, ultrasonically mixing for 30min to obtain a mixed solution a, adding 0.4g of polyvinylpyrrolidone and 100mL of absolute ethyl alcohol into a reaction kettle, heating to 60 ℃ under the protection of nitrogen, adding the mixed solution a and 0.1g of azodiisobutyronitrile, carrying out heat preservation stirring reaction for 24h, cooling to room temperature after the reaction is finished, separating products under the action of an external magnetic field, and respectively using distilled water, methanol and acetic acid according to a volume ratio of 8:2, flushing the mixed solution until the eluent is detected by liquid chromatography-mass spectrometry to be free of biuret, and finally drying at 60 ℃ to obtain the magnetic impurity-removing component.
The surface-modified magnetic carrier is prepared by the following steps:
mixing 2g of magnetic carrier with 40mL of distilled water, adding 2mL of oleic acid under nitrogen protection at 80 ℃, stirring for 30min, cooling to 50 ℃, adding 2.5g of polyethylene glycol, carrying out ultrasonic treatment for 15min, carrying out suction filtration, washing a filter cake, and drying to obtain the surface modified magnetic carrier, wherein the molecular weight of the polyethylene glycol is 6000.
The magnetic carrier is specifically prepared by the following steps:
will be 0.2g Fe 3 O 4 The nano particles and 200mL of ethanol solution with the volume fraction of 80% are ultrasonically mixed for 10min, then 5mL of 28wt% ammonia water is added, 1.5mL of tetraethoxysilane is dropwise added after stirring for 10min, after the dropwise adding is finished, the reaction is carried out for 12h at 45 ℃ under the stirring condition of the rotating speed of 400r/min, the magnetic separation is carried out, the collection is carried out, the absolute ethanol and the deionized water are alternately washed for 3 times, and the magnetic carrier is obtained after freeze drying.
The functional monomer is prepared by the following steps:
adding 0.1mol of acrylamide, 0.1mol of o-hydroxybenzaldehyde and 200mL of absolute ethyl alcohol into a flask, heating to reflux for reaction for 10h, and removing the absolute ethyl alcohol by rotary evaporation after the reaction is finished.
Example 2
The magnetic impurity removing component is prepared by the following steps:
uniformly mixing 0.1g of biuret, 10mL of methanol and 10mL of deionized water, adding 0.6g of methacrylic acid, stirring for 30min, adding 0.5g of functional monomer, 3.4g of ethylene glycol dimethacrylate and 1.3g of surface modified magnetic carrier, ultrasonically mixing for 30min to obtain a mixed solution a, adding 0.4g of polyvinylpyrrolidone and 100mL of absolute ethyl alcohol into a reaction kettle, heating to 60 ℃ under the protection of nitrogen, adding the mixed solution a and 0.1g of azodiisobutyronitrile, carrying out heat preservation stirring reaction for 24h, cooling to room temperature after the reaction is finished, separating products under the action of an external magnetic field, and respectively using distilled water, methanol and acetic acid according to a volume ratio of 8:2, flushing the mixed solution until the eluent is detected by liquid chromatography-mass spectrometry to be free of biuret, and finally drying at 60 ℃ to obtain the magnetic impurity-removing component.
The surface-modified magnetic carrier is prepared by the following steps:
mixing 2g of magnetic carrier with 40mL of distilled water, adding 2mL of oleic acid under nitrogen protection at 80 ℃, stirring for 30min, cooling to 50 ℃, adding 3.4g of polyethylene glycol, carrying out ultrasonic treatment for 15min, carrying out suction filtration, washing a filter cake, and drying to obtain the surface modified magnetic carrier, wherein the molecular weight of the polyethylene glycol is 6000.
The magnetic carrier is specifically prepared by the following steps:
will be 0.2g Fe 3 O 4 The nano particles and 200mL of ethanol solution with the volume fraction of 80% are ultrasonically mixed for 10min, then 5mL of 28wt% ammonia water is added, 1.5mL of tetraethoxysilane is dropwise added after stirring for 10min, after the dropwise adding is finished, the reaction is carried out for 12h at 45 ℃ under the stirring condition of 500r/min, the magnetic separation is carried out, the collection is carried out, the absolute ethanol and the deionized water are alternately used for washing for 3 times, and the magnetic carrier is obtained after freeze drying.
The functional monomer is prepared by the following steps:
adding 0.11mol of acrylamide, 0.1mol of o-hydroxybenzaldehyde and 200mL of absolute ethyl alcohol into a flask, heating to reflux for reaction for 12h, and removing the absolute ethyl alcohol by rotary evaporation after the reaction is finished.
Comparative example 1
On the basis of example 1, only the functional monomer of example 1 was removed, and the remaining raw materials and the preparation process were the same as in example 1.
Comparative example 2
Based on example 1, only the surface-modified magnetic carrier in example 1 was replaced with a magnetic carrier, and the rest of the raw materials and the preparation process were the same as in example 1.
Example 3
The preparation method of the urea solution for the vehicle comprises the following steps:
urea particles and ultrapure water are mixed according to a mass ratio of 32:68, adding the mixture into a stirring tank, stirring and mixing for 30min at 25 ℃ and a rotating speed of 200r/min to obtain a crude product, adding the magnetic impurity removing component of the embodiment 1, continuously stirring for 5min, and separating the magnetic impurity removing component by an external magnetic field to obtain the urea solution for the vehicle.
Wherein, the dosage of the magnetic impurity removing component is 1% of the crude product mass, and the ultrapure water is required to meet the technical requirement of pure water in GB29518-2013 (urea aqueous solution of Nitrogen oxide reducing agent of Diesel engine (AUS 32)) standard.
Example 4
The preparation method of the urea solution for the vehicle comprises the following steps:
urea particles and ultrapure water are mixed according to a mass ratio of 33:67, stirring and mixing for 25min at 30 ℃ and 250r/min to obtain a crude product, adding the magnetic impurity removing component of the embodiment 2, continuously stirring for 8min, and separating the magnetic impurity removing component by an external magnetic field to obtain the urea solution for the vehicle.
Wherein, the dosage of the magnetic impurity removing component is 1.5% of the crude product mass, and the ultrapure water is required to meet the technical requirement of pure water in GB29518-2013 (urea aqueous solution of Nitrogen oxide reducing agent of Diesel engine (AUS 32)) standard.
Example 5
The preparation method of the urea solution for the vehicle comprises the following steps:
urea particles and ultrapure water are mixed according to a mass ratio of 35:65, adding the mixture into a stirring tank, stirring and mixing for 30min at 35 ℃ and a rotating speed of 300r/min to obtain a crude product, then adding the magnetic impurity removing component of the embodiment 2, continuously stirring for 10min, and separating the magnetic impurity removing component by an external magnetic field to obtain the urea solution for the vehicle.
Wherein, the dosage of the magnetic impurity removing component is 2% of the crude product mass, and the ultrapure water is required to meet the technical requirement of pure water in GB29518-2013 (urea aqueous solution of Nitrogen oxide reducing agent of Diesel engine (AUS 32)) standard.
Comparative example 3
Based on example 1, only the magnetic impurity removing component of example 3 was replaced with the material of comparative example 1, and the remaining raw materials and the production process were the same as in example 3.
Comparative example 4
Based on example 1, only the magnetic impurity removing component of example 3 was replaced with the material of comparative example 2, and the remaining raw materials and the preparation process were the same as those of example 3.
The urea solutions for vehicles obtained in examples 3 to 5 and comparative examples 3 to 4 were tested for biuret, insoluble matter and metal ion content by reference to standard GB29518-2013 annex C, E, G, and were tested according to the method of HJ451-2008 "environmental protection product technical requirements diesel vehicle emission aftertreatment device", with nitrogen oxide conversion, and the results are shown in table 1:
TABLE 1
| Project | Example 3 | Example 4 | Example 5 | Comparative example 3 | Comparative example 4 |
| Biuret (mass fraction)% | 0.009 | 0.008 | 0.005 | 0.18 | 0.23 |
| insoluble/(mg.L) -1 ) | 1.07 | 0.92 | 0.74 | 3.2 | 2.8 |
| calcium/(mg.L) -1 ) | 0.01 | 0.008 | 0.006 | 0.02 | 0.04 |
| iron/(mg.L) -1 ) | 0.003 | 0.002 | 0.001 | 0.01 | 0.02 |
| Copper (mg.L) -1 ) | 0.002 | 0.001 | 0.001 | 0.009 | 0.12 |
| Conversion of oxynitride (%) | 96.5 | 96.9 | 97.2 | 94.1 | 92.8 |
As can be seen from table 1, the urea solutions for vehicles obtained in example 3, example 4, and example 5 have higher purity, higher conversion rate of oxynitride, and greater application value than those of comparative examples 3 and 4.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. The preparation method of the urea solution for the vehicle is characterized by comprising the following steps of:
urea particles and ultrapure water are mixed according to the mass ratio of 32-35: adding 65-68 into a stirring tank, stirring and mixing at 25-35deg.C for 20-30min to obtain crude product, adding magnetic impurity removing component, stirring for 5-10min, and separating magnetic impurity removing component by external magnetic field to obtain urea solution for vehicle;
wherein, the magnetic impurity removing component is specifically prepared by the following steps:
uniformly mixing biuret, methanol and deionized water, adding methacrylic acid, stirring for 10-30min, adding functional monomer, glycol dimethacrylate and surface modified magnetic carrier, ultrasonically mixing for 30min to obtain mixed solution a, adding polyvinylpyrrolidone and absolute ethyl alcohol into a reaction kettle, heating to 60 ℃ under the protection of nitrogen, adding the mixed solution a and azodiisobutyronitrile, carrying out heat preservation and stirring for reaction for 24h, cooling to room temperature, separating products under the action of an external magnetic field, and respectively using distilled water, methanol and acetic acid according to the volume ratio of 8:2, flushing the mixed solution until the eluent is detected by liquid chromatography-mass spectrometry to be free of biuret, and finally drying at 60 ℃ to obtain the magnetic impurity-removing component.
2. The method for preparing a urea solution for vehicles according to claim 1, wherein the amount of the magnetic impurity removing component is 1-2% of the mass of the crude product.
3. The method for preparing a urea solution for vehicles according to claim 1, wherein the amount ratio of biuret, methanol, deionized water, functional monomers, methacrylic acid, ethylene glycol dimethacrylate, surface-modified magnetic carrier, polyvinylpyrrolidone, absolute ethanol and azobisisobutyronitrile is 0.1g:10mL:10mL:0.3-0.5g:0.4-0.6g:2.8-3.4g:0.9-1.3g:0.4g:100mL:0.1g.
4. The method for preparing a urea solution for vehicles according to claim 1, wherein the surface-modified magnetic carrier is prepared by the steps of:
mixing the magnetic carrier with distilled water, adding oleic acid under nitrogen protection at 80 ℃, stirring for 30min, cooling to 50 ℃, adding polyethylene glycol, performing ultrasonic treatment for 15min, performing suction filtration, washing a filter cake, and drying to obtain the surface modified magnetic carrier.
5. The method for preparing a urea solution for vehicles according to claim 4, wherein the ratio of the amount of the magnetic carrier, distilled water, oleic acid and polyethylene glycol is 2g:40mL:2mL:2.5-3.4g, and the molecular weight of polyethylene glycol is 6000.
6. The method for preparing a urea solution for vehicles according to claim 4, wherein the magnetic carrier is nano ferroferric oxide with a silica coating layer supported on the surface.
7. The method for preparing a urea solution for vehicles according to claim 1, characterized in that the functional monomer is prepared by the following steps:
adding acrylamide, o-hydroxybenzaldehyde and absolute ethyl alcohol into a flask, heating to reflux reaction for 10-12h, and removing the absolute ethyl alcohol by rotary evaporation after the reaction is finished.
8. The method for preparing a urea solution for vehicles according to claim 7, wherein the molar ratio of acrylamide to o-hydroxybenzaldehyde is 1-1.1:1.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090057230A1 (en) * | 2007-08-29 | 2009-03-05 | Colonial Chemical Company | Method and system for removing inpurities from a urea solution |
| CN105921014A (en) * | 2016-05-10 | 2016-09-07 | 南宁市夏阳化工科技有限责任公司 | Preparing method for urea solution used for vehicles |
| CN106039996A (en) * | 2016-06-28 | 2016-10-26 | 许江煌 | Adblue and preparation method thereof |
| CN106064020A (en) * | 2016-06-28 | 2016-11-02 | 许江煌 | A kind of preparation method of urea for vehicle |
| CN107051204A (en) * | 2017-05-09 | 2017-08-18 | 东莞蔚蓝环保科技有限公司 | A kind of preparation technology of urea for vehicle solution |
| CN108993137A (en) * | 2018-08-15 | 2018-12-14 | 罗永平 | A kind of urea for vehicle solution and preparation method thereof |
| CN109012156A (en) * | 2018-08-15 | 2018-12-18 | 罗永平 | A kind of anti-clogging urea for vehicle solution and preparation method thereof |
| CN109939566A (en) * | 2019-04-16 | 2019-06-28 | 灵谷化工集团有限公司 | A kind of low temperature resistant urea for vehicle solution of crystallization-preventive and preparation method thereof |
| CN112110835A (en) * | 2020-09-30 | 2020-12-22 | 河南弘康环保科技有限公司 | Automobile urea capable of preventing urea biuret, cyanuric acid and melamine intermediate products from being generated and preparation method thereof |
| CN115999362A (en) * | 2022-12-13 | 2023-04-25 | 江苏可兰素环保科技有限公司 | Production process of urea solution for vehicles |
-
2023
- 2023-10-18 CN CN202311351377.7A patent/CN117417273B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090057230A1 (en) * | 2007-08-29 | 2009-03-05 | Colonial Chemical Company | Method and system for removing inpurities from a urea solution |
| CN105921014A (en) * | 2016-05-10 | 2016-09-07 | 南宁市夏阳化工科技有限责任公司 | Preparing method for urea solution used for vehicles |
| CN106039996A (en) * | 2016-06-28 | 2016-10-26 | 许江煌 | Adblue and preparation method thereof |
| CN106064020A (en) * | 2016-06-28 | 2016-11-02 | 许江煌 | A kind of preparation method of urea for vehicle |
| CN107051204A (en) * | 2017-05-09 | 2017-08-18 | 东莞蔚蓝环保科技有限公司 | A kind of preparation technology of urea for vehicle solution |
| CN108993137A (en) * | 2018-08-15 | 2018-12-14 | 罗永平 | A kind of urea for vehicle solution and preparation method thereof |
| CN109012156A (en) * | 2018-08-15 | 2018-12-18 | 罗永平 | A kind of anti-clogging urea for vehicle solution and preparation method thereof |
| CN109939566A (en) * | 2019-04-16 | 2019-06-28 | 灵谷化工集团有限公司 | A kind of low temperature resistant urea for vehicle solution of crystallization-preventive and preparation method thereof |
| CN112110835A (en) * | 2020-09-30 | 2020-12-22 | 河南弘康环保科技有限公司 | Automobile urea capable of preventing urea biuret, cyanuric acid and melamine intermediate products from being generated and preparation method thereof |
| CN115999362A (en) * | 2022-12-13 | 2023-04-25 | 江苏可兰素环保科技有限公司 | Production process of urea solution for vehicles |
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