CN117589759B - Method for rapidly detecting metal content in urea aqueous solution of nitrogen oxide reducing agent - Google Patents
Method for rapidly detecting metal content in urea aqueous solution of nitrogen oxide reducing agent Download PDFInfo
- Publication number
- CN117589759B CN117589759B CN202410057765.2A CN202410057765A CN117589759B CN 117589759 B CN117589759 B CN 117589759B CN 202410057765 A CN202410057765 A CN 202410057765A CN 117589759 B CN117589759 B CN 117589759B
- Authority
- CN
- China
- Prior art keywords
- detection
- aqueous solution
- chitosan
- surface modification
- urea
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 125
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000004202 carbamide Substances 0.000 title claims abstract description 64
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 45
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 24
- 239000002184 metal Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 24
- 229920001661 Chitosan Polymers 0.000 claims abstract description 75
- 238000001514 detection method Methods 0.000 claims abstract description 67
- 239000004005 microsphere Substances 0.000 claims abstract description 58
- 230000004048 modification Effects 0.000 claims abstract description 41
- 238000012986 modification Methods 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000003756 stirring Methods 0.000 claims abstract description 34
- 239000008139 complexing agent Substances 0.000 claims abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 32
- 239000008367 deionised water Substances 0.000 claims abstract description 30
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 28
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 13
- 239000004353 Polyethylene glycol 8000 Substances 0.000 claims abstract description 13
- 239000008103 glucose Substances 0.000 claims abstract description 13
- 235000019446 polyethylene glycol 8000 Nutrition 0.000 claims abstract description 13
- 229940085678 polyethylene glycol 8000 Drugs 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims abstract description 9
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 8
- AMMWFYKTZVIRFN-UHFFFAOYSA-N sodium 3-hydroxy-4-[(1-hydroxynaphthalen-2-yl)diazenyl]-7-nitronaphthalene-1-sulfonic acid Chemical compound [Na+].C1=CC=CC2=C(O)C(N=NC3=C4C=CC(=CC4=C(C=C3O)S(O)(=O)=O)[N+]([O-])=O)=CC=C21 AMMWFYKTZVIRFN-UHFFFAOYSA-N 0.000 claims abstract description 8
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 6
- 230000010355 oscillation Effects 0.000 claims description 37
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000003981 vehicle Substances 0.000 claims description 21
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 15
- 239000001263 FEMA 3042 Substances 0.000 claims description 15
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 15
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 15
- 229940033123 tannic acid Drugs 0.000 claims description 15
- 235000015523 tannic acid Nutrition 0.000 claims description 15
- 229920002258 tannic acid Polymers 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 238000001694 spray drying Methods 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 11
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 9
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 8
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 8
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 8
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 8
- 239000005642 Oleic acid Substances 0.000 claims description 8
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 8
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 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
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 239000007853 buffer solution Substances 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 238000000643 oven drying Methods 0.000 claims description 2
- ZRBROGSAUIUIJE-UHFFFAOYSA-N azanium;azane;chloride Chemical compound N.[NH4+].[Cl-] ZRBROGSAUIUIJE-UHFFFAOYSA-N 0.000 claims 1
- 229910021645 metal ion Inorganic materials 0.000 abstract description 8
- 150000002739 metals Chemical class 0.000 abstract description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 8
- 230000000536 complexating effect Effects 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- -1 aluminum ions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000003926 complexometric titration Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005008 domestic process Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/82—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a precipitate or turbidity
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
- G01N2021/0106—General arrangement of respective parts
- G01N2021/0112—Apparatus in one mechanical, optical or electronic block
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Plasma & Fusion (AREA)
- Engineering & Computer Science (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention discloses a method for rapidly detecting metal content in urea aqueous solution of nitrogen oxide reducing agent, belonging to the technical field of metal ion detection, wherein the detection method comprises the following steps: preparing an auxiliary complexing agent, preparing a detection solution and detecting; the preparation auxiliary complexing agent comprises the following steps: preparing crosslinked chitosan microspheres, performing primary surface modification and secondary surface modification; the detection liquid is prepared by mixing EDTA-2Na, 12-crown ether-4, an auxiliary complexing agent, chrome black T, glycerol, triethanolamine, polyethylene glycol 8000, glucose, absolute ethyl alcohol and deionized water, and stirring at normal temperature to obtain the detection liquid; the invention can complete the rapid detection of all metals in the urea aqueous solution of the nitrogen oxide reducing agent, has little influence on the detection due to temperature, and has good stability of the detection liquid used in the detection.
Description
Technical Field
The invention relates to the technical field of metal ion detection, in particular to a method for rapidly detecting metal content in urea aqueous solution of a nitrogen oxide reducing agent.
Background
Diesel vehicles such as heavy trucks and buses are required to reach the national six-emission standard, a proper Selective Catalytic Reduction (SCR) system is required to be used for treating tail gas, and urea solution is required to be used for treating nitrogen oxides in the tail gas in the SCR system. Therefore, the urea solution for the vehicle is an indispensable product for the heavy trucks and buses to reach the national sixth emission standard.
The urea for the vehicle is urea aqueous solution with the mass concentration of 32.5% and the solvent of ultrapure water, and the production raw materials are special raw materials for the urea for the vehicle and the ultrapure water, and the key point is the purity of the raw materials. From the production process, the purity requirement of the urea for the vehicle on the raw material is higher than the requirement of the general industry, but the domestic process can meet the practical application requirement at present.
The domestic vehicle urea is mainly purified from industrial urea, and the main principle is as follows: at 70-75 ℃, urea is hydrolyzed in aqueous solution; at a temperature below 30 ℃, urea is recrystallized from the aqueous solution again; the purity of the urea is greatly improved once every hydrolysis crystallization, and the standard requirement of the urea for vehicles can be met by generally utilizing one-time industrial primary urea hydrolysis crystallization, wherein the yield ratio is 1.5:1.
Because the SCR catalyst carrier is extremely easy to be poisoned by metal ions and loses the catalytic effect, the vehicular urea solution needs to use tertiary water with the conductivity less than or equal to 0.50mS/m at 25 ℃ which accords with GB/T6682. The urea solution for vehicles can start to freeze below-11 ℃, and can be completely frozen at-20 ℃ in actual use. At present, the solution is mainly prevented from solidifying by means of adding a modifier to reduce the solidifying point of the solution, adding a heating device and the like.
For the detection of metal ions in the urea for the vehicle, the method in the urea aqueous solution (AUS 32) of the nitrogen oxide reducer of the diesel engine specified in GB 29518 is mainly used for detecting the metal ion content by adopting an inductively coupled plasma emission spectrometry, but detection equipment used by the method is expensive, most of vehicle urea production enterprises do not have the detection equipment, and the detection equipment can be sent to a third party for detection, but the third party detection is high in cost and long in detection time, and the detection result cannot be timely and quickly obtained, so that most enterprises do not detect the metal ions in the urea for the vehicle in the actual production process, consumers lack detection means, and the detection of the vehicle urea in the market is difficult, and the market supervision difficulty is high. Therefore, finding a method capable of rapidly judging whether the vehicle urea contains metal ions is an urgent problem to be solved in the current vehicle urea field.
In order to solve the above problems, the most commonly used method is to use ethylenediamine tetraacetic acid (EDTA) complexometric titration to determine whether or not the vehicle urea contains metal ions by color change. However, EDTA complexation titration has the following problems: EDTA has limited complexing ability and poor complexing ability for alkali metal ions; the color change is slow in an environment with lower temperature because of large temperature influence; EDTA complexation titrant has poor stability.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a method for rapidly detecting the metal content in the urea aqueous solution of the nitrogen oxide reducing agent, which can complete the rapid detection of all metals in the urea aqueous solution of the nitrogen oxide reducing agent, and has the advantages of little influence by temperature during the detection and good stability of detection liquid used in the detection.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for rapidly detecting the metal content in urea aqueous solution of nitrogen oxide reducing agent comprises the following steps: preparing an auxiliary complexing agent, preparing a detection solution and detecting;
the preparation auxiliary complexing agent comprises the following steps: preparing crosslinked chitosan microspheres, performing primary surface modification and secondary surface modification;
the preparation of the crosslinked chitosan microsphere comprises the steps of mixing chitosan, glacial acetic acid and deionized water, and uniformly stirring at the stirring speed of 100-200rpm at normal temperature to obtain a chitosan solution; spray drying the chitosan solution, controlling the inlet temperature in spray drying to be 180-200 ℃ and the outlet temperature to be 80-90 ℃, and obtaining chitosan microspheres after spray drying; mixing chitosan microsphere with ethyl acetate, stirring at 50-60deg.C at 100-200rpm for 20-30min, dripping glutaraldehyde, stirring for 1.5-2 hr, filtering, washing the residue with anhydrous ethanol for 2-4 times, and oven drying at 70-80deg.C to obtain crosslinked chitosan microsphere;
in the preparation of the crosslinked chitosan microsphere, the mass volume ratio of chitosan, glacial acetic acid and deionized water is 22-25g:20-22g:1000-1100mL;
the mass volume ratio of the chitosan microsphere to the ethyl acetate to the glutaraldehyde is 20-25g:900-1000mL:10-12mL;
the dropping speed of glutaraldehyde is 0.5-0.6mL/min;
the primary surface modification, after mixing ammonia water, oleic acid, N-vinyl pyrrolidone and deionized water, carrying out ultrasonic oscillation at normal temperature, controlling the frequency of ultrasonic oscillation to be 20-30KHz for 1-2h, adding the crosslinked chitosan microsphere, continuing ultrasonic oscillation at normal temperature, controlling the frequency of ultrasonic oscillation to be 20-30KHz for 3-4h, filtering after ultrasonic oscillation is finished, cleaning filter residues with deionized water for 3-4 times, and drying at 110-120 ℃ to obtain the chitosan microsphere with primary surface modification;
in the primary surface modification, the mass-volume ratio of ammonia water, oleic acid, N-vinyl pyrrolidone, deionized water and crosslinked chitosan microspheres is 90-95mL:100-110mL:4-5mL:250-280mL:100-120g;
the mass concentration of the ammonia water is 25%;
mixing the chitosan microspheres subjected to primary surface modification and the tannic acid aqueous solution, performing ultrasonic oscillation at normal temperature, controlling the frequency of ultrasonic oscillation to be 20-30KHz for 4-6min, filtering after ultrasonic oscillation is finished, cleaning filter residues with deionized water for 3-4 times, and drying at 110-120 ℃ to obtain an auxiliary complexing agent;
in the secondary surface modification, the mass volume ratio of the chitosan microsphere subjected to the primary surface modification to the tannic acid aqueous solution is 100-120g:400-450mL;
the mass concentration of the tannic acid aqueous solution is 7-8%;
the detection liquid is prepared by mixing EDTA-2Na, 12-crown ether-4, an auxiliary complexing agent, chrome black T, glycerol, triethanolamine, polyethylene glycol 8000, glucose, absolute ethyl alcohol and deionized water, and stirring at a stirring speed of 100-200rpm for 50-60min at normal temperature to obtain the detection liquid;
in the preparation detection liquid, the mass volume ratio of EDTA-2Na, 12-crown ether-4, auxiliary complexing agent, chrome black T, glycerol, triethanolamine, polyethylene glycol 8000, glucose, absolute ethyl alcohol and deionized water is 7.5-8g:1-1.2mL:8-9g:3-3.5g:3-4mL:4-5mL:2.5-3g:2-3g:100-120mL:900-950mL;
and (3) detecting, namely taking 100mL of urea for the vehicle to be detected, firstly adding 3-5mL of ammonia water-ammonium chloride buffer solution with pH=10, then dropwise adding 6-7 drops of detection liquid, and uniformly mixing.
Compared with the prior art, the invention has the beneficial effects that:
(1) The method for rapidly detecting the metal content in the nitrogen oxide reducing agent urea aqueous solution can complete rapid detection of all metals in the nitrogen oxide reducing agent urea aqueous solution, and the urea aqueous solution prepared by using secondary water is detected at 25 ℃, and the time required for the color of the urea aqueous solution is 7-8s when the color of the urea aqueous solution is not changed any more;
(2) The rapid detection method of the metal content in the urea aqueous solution of the nitrogen oxide reducing agent has little influence by temperature during detection, the urea aqueous solution prepared by using the secondary water is detected at the temperature of 5 ℃, and the time required for the color of the urea aqueous solution to be no longer changed is 15-16s;
(3) According to the rapid detection method for the metal content in the urea aqueous solution of the nitrogen oxide reducing agent, disclosed by the invention, the stability of the detection liquid used in detection is good, the detection liquid used is sealed and placed for 30 days at the temperature of 25 ℃, and no sediment is generated;
(4) According to the rapid detection method for the metal content in the urea aqueous solution of the nitrogen oxide reducing agent, disclosed by the invention, the complex by only using EDTA is avoided by using tannic acid and 12-crown ether-4 to be matched, the detection result is inaccurate due to the fact that the complexing capability of EDTA is insufficient, and the electron transport capability can be improved by attaching tannic acid to the chitosan microsphere subjected to anion surface modification and utilizing anion interaction while the complexing speed is improved, so that the stability of the detection solution can be improved.
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 rapidly detecting the metal content in urea aqueous solution of nitrogen oxide reducing agent specifically comprises the following steps:
1. preparing an auxiliary complexing agent:
(1) Preparing crosslinked chitosan microspheres: mixing 22g of chitosan, 20g of glacial acetic acid and 1000mL of deionized water, and uniformly stirring at the stirring speed of 100rpm at normal temperature to obtain a chitosan solution; spray drying the chitosan solution, controlling the inlet temperature to be 180 ℃ and the outlet temperature to be 80 ℃ in spray drying, and obtaining chitosan microspheres after spray drying; adding 900mL of ethyl acetate into 20g of chitosan microspheres, mixing, stirring at 50 ℃ for 20min at a stirring speed of 100rpm, dripping 10mL of glutaraldehyde, controlling the dripping speed to be 0.5mL/min, continuously stirring for 1.5h after dripping, filtering, washing filter residues with absolute ethyl alcohol for 2 times, and drying at 70 ℃ to obtain crosslinked chitosan microspheres;
(2) Primary surface modification: mixing 90mL of ammonia water, 100mL of oleic acid, 4mL of N-vinyl pyrrolidone and 250mL of deionized water, performing ultrasonic oscillation at normal temperature, controlling the frequency of ultrasonic oscillation to be 20KHz for 1h, adding 100g of crosslinked chitosan microspheres, continuing ultrasonic oscillation at normal temperature, controlling the frequency of ultrasonic oscillation to be 20KHz for 3h, filtering after ultrasonic oscillation is finished, cleaning filter residues with deionized water for 3 times, and drying at 110 ℃ to obtain the chitosan microspheres with one-time surface modification;
the mass concentration of the ammonia water is 25%;
(3) Secondary surface modification: mixing 100g of chitosan microsphere with one-time surface modification and 400mL of tannic acid aqueous solution with mass concentration of 7%, performing ultrasonic oscillation at normal temperature, controlling the frequency of ultrasonic oscillation to be 20KHz and the time to be 4min, filtering after ultrasonic oscillation is finished, cleaning filter residues with deionized water for 3 times, and drying at 110 ℃ to obtain an auxiliary complexing agent;
2. preparing a detection solution: mixing 7.5g of EDTA-2Na, 1mL of 12-crown ether-4, 8g of auxiliary complexing agent, 3g of chrome black T, 3mL of glycerol, 4mL of triethanolamine, 2.5g of polyethylene glycol 8000, 2g of glucose, 100mL of absolute ethyl alcohol and 900mL of deionized water, and stirring at a stirring speed of 100rpm for 50min at normal temperature to obtain a detection solution;
3. and (3) detection: taking 100mL of urea for a vehicle to be tested, firstly adding 3mL of ammonia water-ammonium chloride buffer solution with pH=10, then dripping 6 drops of detection solution, and uniformly mixing.
Example 2
A method for rapidly detecting the metal content in urea aqueous solution of nitrogen oxide reducing agent specifically comprises the following steps:
1. preparing an auxiliary complexing agent:
(1) Preparing crosslinked chitosan microspheres: mixing 24g of chitosan, 21g of glacial acetic acid and 1050mL of deionized water, and uniformly stirring at a stirring speed of 150rpm at normal temperature to obtain a chitosan solution; spray drying the chitosan solution, controlling the inlet temperature to be 190 ℃ and the outlet temperature to be 85 ℃ in spray drying, and obtaining chitosan microspheres after spray drying; mixing 22g of chitosan microspheres with 950mL of ethyl acetate, stirring at 55 ℃ for 25min at a stirring speed of 150rpm, dripping 11mL of glutaraldehyde, controlling the dripping speed to be 0.5mL/min, continuously stirring for 1.5h after dripping, filtering, washing filter residues with absolute ethyl alcohol for 3 times, and drying at 75 ℃ to obtain crosslinked chitosan microspheres;
(2) Primary surface modification: mixing 92mL of ammonia water, 105mL of oleic acid, 4.5mL of N-vinyl pyrrolidone and 260mL of deionized water, performing ultrasonic oscillation at room temperature, controlling the frequency of ultrasonic oscillation to be 25KHz, the time to be 1.5h, adding 110g of crosslinked chitosan microsphere, continuing ultrasonic oscillation at room temperature, controlling the frequency of ultrasonic oscillation to be 25KHz, the time to be 3.5h, filtering after ultrasonic oscillation is finished, cleaning filter residues with deionized water for 3 times, and drying at 115 ℃ to obtain the chitosan microsphere with one-time surface modification;
the mass concentration of the ammonia water is 25%;
(3) Secondary surface modification: mixing 110g of chitosan microsphere with one-time surface modification and 420mL of tannic acid aqueous solution with mass concentration of 7.5%, performing ultrasonic oscillation at normal temperature, controlling the frequency of ultrasonic oscillation to be 25KHz for 5min, filtering after ultrasonic oscillation is finished, cleaning filter residues with deionized water for 3 times, and drying at 115 ℃ to obtain an auxiliary complexing agent;
2. preparing a detection solution: 7.8g of EDTA-2Na, 1.1mL of 12-crown ether-4, 8.5g of auxiliary complexing agent, 3.2g of chrome black T, 3.5mL of glycerol, 4.5mL of triethanolamine, 2.8g of polyethylene glycol 8000, 2.5g of glucose, 110mL of absolute ethyl alcohol and 920mL of deionized water are mixed, and then stirred at a stirring speed of 150rpm for 55min at normal temperature to obtain a detection solution;
3. and (3) detection: taking 100mL of urea for a vehicle to be tested, firstly adding 4mL of ammonia water-ammonium chloride buffer solution with pH=10, then dripping 6 drops of detection solution, and uniformly mixing.
Example 3
A method for rapidly detecting the metal content in urea aqueous solution of nitrogen oxide reducing agent specifically comprises the following steps:
1. preparing an auxiliary complexing agent:
(1) Preparing crosslinked chitosan microspheres: mixing 25g of chitosan, 22g of glacial acetic acid and 1100mL of deionized water, and uniformly stirring at the stirring speed of 200rpm at normal temperature to obtain a chitosan solution; spray drying the chitosan solution, controlling the inlet temperature to be 200 ℃ and the outlet temperature to be 90 ℃ in spray drying, and obtaining chitosan microspheres after spray drying; mixing 25g of chitosan microspheres with 1000mL of ethyl acetate, stirring at 60 ℃ for 30min at a stirring speed of 200rpm, dripping 12mL of glutaraldehyde, controlling the dripping speed to be 0.6mL/min, continuously stirring for 2h after dripping, filtering, washing filter residues with absolute ethyl alcohol for 4 times, and drying at 80 ℃ to obtain crosslinked chitosan microspheres;
(2) Primary surface modification: mixing 95mL of ammonia water, 110mL of oleic acid, 5mL of N-vinyl pyrrolidone and 280mL of deionized water, performing ultrasonic oscillation at normal temperature, controlling the frequency of ultrasonic oscillation to be 30KHz for 2 hours, adding 120g of crosslinked chitosan microspheres, continuing ultrasonic oscillation at normal temperature, controlling the frequency of ultrasonic oscillation to be 30KHz for 4 hours, filtering after ultrasonic oscillation is finished, cleaning filter residues with deionized water for 4 times, and drying at 120 ℃ to obtain the chitosan microspheres with one-time surface modification;
the mass concentration of the ammonia water is 25%;
(3) Secondary surface modification: mixing 120g of chitosan microsphere with one-time surface modification and 450mL of tannic acid aqueous solution with mass concentration of 8%, performing ultrasonic oscillation at normal temperature, controlling the frequency of ultrasonic oscillation to be 30KHz and the time to be 6min, filtering after ultrasonic oscillation is finished, cleaning filter residues with deionized water for 4 times, and drying at 120 ℃ to obtain an auxiliary complexing agent;
2. preparing a detection solution: 8g of EDTA-2Na, 1.2mL of 12-crown ether-4, 9g of auxiliary complexing agent, 3.5g of chrome black T, 4mL of glycerol, 5mL of triethanolamine, 3g of polyethylene glycol 8000, 3g of glucose, 120mL of absolute ethyl alcohol and 950mL of deionized water are mixed, and then stirred at a stirring speed of 200rpm for 60min at normal temperature to obtain a detection solution;
3. and (3) detection: taking 100mL of urea for a vehicle to be tested, firstly adding 5mL of ammonia water-ammonium chloride buffer solution with pH=10, then dropwise adding 7 drops of detection solution, and uniformly mixing.
Comparative example 1
In order to verify the effect of preparing crosslinked chitosan microspheres and primary surface modification in the preparation of the auxiliary complexing agent in step 1, the method of example 2 was modified in that: the step of preparing the auxiliary complexing agent in step 1 is omitted, the addition of the auxiliary complexing agent, polyethylene glycol 8000 and glucose is omitted in the step of detecting in step 3, and 2g of tannic acid is additionally added.
Test example 1
At 25℃a urea aqueous solution having a mass concentration of 32.5% was prepared using tap water having a conductivity of 10mS/m instead of tertiary water, and then rapidly examined by the methods of examples 1-3 and comparative example 1, respectively, and after the completion of the dropwise addition, stirring was carried out at a stirring speed of 100rpm, and the time required for the color of the urea aqueous solution to no longer change after the completion of the dropwise addition was recorded, and the results were recorded as follows:
test example 2
At 5℃a urea aqueous solution having a mass concentration of 32.5% was prepared using tap water having a conductivity of 10mS/m instead of tertiary water, and then rapidly examined by the methods of examples 1-3 and comparative example 1, respectively, and after the completion of the dropwise addition, stirring was carried out at a stirring speed of 100rpm, and the time required for the color of the urea aqueous solution to no longer change after the completion of the dropwise addition was recorded, and the results were recorded as follows:
as can be seen from the results of test examples 1-2, the addition of the auxiliary complexing agent, polyethylene glycol 8000 and glucose can improve the detection speed of metal in the urea aqueous solution of the nitrogen oxide reducing agent and reduce the influence of temperature on the detection speed;
the preparation method of the auxiliary complexing agent comprises the steps of carrying out primary surface modification and secondary surface modification on the crosslinked chitosan microsphere, wherein the primary surface modification is carried out anion surface modification on the crosslinked chitosan microsphere by using ammonia water, oleic acid and N-vinyl pyrrolidone, and the secondary surface modification is carried out coating on the chitosan microsphere after the primary surface modification by using tannic acid;
wherein, crosslinked chitosan microsphere is as carrier, tannic acid can be loaded, tannic acid cooperates with EDTA-2Na, 12-crown ether-4, complex calcium, iron, copper, zinc, chromium, nickel, magnesium, sodium, potassium and aluminum ions in urea, make up for the deficiency of complexing by using EDTA only, avoid the incomplete condition of detection, after carrying out surface modification on crosslinked chitosan microsphere once, can improve the dispersion capacity of crosslinked chitosan microsphere, can also improve the electron transmission capacity of crosslinked chitosan microsphere, thereby improving the formation speed of complex, reducing the influence of temperature on the formation speed of complex, polyethylene glycol 8000 and glucose can be used as suspension stabilizer, improve the dispersion capacity of auxiliary complexing agent in detection liquid, and avoid the occurrence of precipitation.
Test example 3
The test solutions prepared in examples 1 to 3 and comparative example 1 were placed under a seal at 25℃for 30 days, and then observed for the formation of precipitate at the bottom, and the observation results were as follows:
from the above results, it can be seen that the addition of the auxiliary complexing agent, polyethylene glycol 8000 and glucose can improve the stability of the detection reagent used in detection, and after the auxiliary complexing agent is added, the auxiliary complexing agent can be stably dispersed in the detection liquid under the action of polyethylene glycol 8000 and glucose, and anions in the surface of the auxiliary complexing agent can also play a role in improving the dispersibility and stability of the detection liquid system.
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 (7)
1. A method for rapidly detecting the metal content in urea aqueous solution of a nitrogen oxide reducing agent is characterized by comprising the following steps: preparing an auxiliary complexing agent, preparing a detection solution and detecting;
the preparation auxiliary complexing agent comprises the following steps: preparing crosslinked chitosan microspheres, performing primary surface modification and secondary surface modification;
the preparation method comprises the steps of preparing crosslinked chitosan microspheres, mixing chitosan, glacial acetic acid and deionized water, and uniformly stirring at normal temperature to obtain a chitosan solution; spray drying the chitosan solution to obtain chitosan microspheres; mixing chitosan microsphere with ethyl acetate, stirring at 50-60deg.C, dripping glutaraldehyde, stirring, filtering, cleaning, and oven drying residue to obtain crosslinked chitosan microsphere;
mixing ammonia water, oleic acid, N-vinyl pyrrolidone and deionized water, performing ultrasonic oscillation at normal temperature, adding crosslinked chitosan microspheres, continuing ultrasonic oscillation at normal temperature, filtering after ultrasonic oscillation is finished, cleaning, and drying filter residues to obtain chitosan microspheres with primary surface modification;
the secondary surface modification is carried out, after the chitosan microsphere and the tannic acid aqueous solution subjected to the primary surface modification are mixed, ultrasonic oscillation is carried out at normal temperature, and after the ultrasonic oscillation is finished, filter, cleaning and drying are carried out on filter residues to obtain an auxiliary complexing agent;
the detection liquid is prepared by mixing EDTA-2Na, 12-crown ether-4, an auxiliary complexing agent, chrome black T, glycerol, triethanolamine, polyethylene glycol 8000, glucose, absolute ethyl alcohol and deionized water, and stirring at normal temperature to obtain the detection liquid;
and (3) detecting, namely taking the urea for the vehicle to be detected, firstly adding ammonia water-ammonium chloride buffer solution, then dropwise adding detection solution, and uniformly mixing.
2. The method for rapidly detecting the metal content in the urea aqueous solution of the nitrogen oxide reducing agent according to claim 1, wherein the mass-volume ratio of chitosan, glacial acetic acid and deionized water in the preparation of the crosslinked chitosan microsphere is 22-25g:20-22g:1000-1100mL.
3. The method for rapidly detecting the metal content in the urea aqueous solution of the nitrogen oxide reducing agent according to claim 1, wherein in the preparation of the crosslinked chitosan microsphere, the mass-volume ratio of the chitosan microsphere, the ethyl acetate and the glutaraldehyde is 20-25g:900-1000mL:10-12mL;
the dripping speed of glutaraldehyde is 0.5-0.6mL/min.
4. The method for rapidly detecting metal content in an aqueous urea solution of a nitrogen oxide reducing agent according to claim 1, wherein in the preparation of the crosslinked chitosan microsphere, the mass-volume ratio of ammonia water, oleic acid, N-vinylpyrrolidone, deionized water and the crosslinked chitosan microsphere is 90-95ml:100-110ml:4-5ml:250-280ml:100-120g in the primary surface modification;
the mass concentration of the ammonia water is 25%.
5. The method for rapidly detecting the metal content in the urea aqueous solution of the nitrogen oxide reducing agent according to claim 1, wherein in the preparation of the crosslinked chitosan microsphere, the mass volume ratio of the chitosan microsphere subjected to primary surface modification to the tannic acid aqueous solution in the secondary surface modification is 100-120g:400-450mL;
the mass concentration of the tannic acid aqueous solution is 7-8%.
6. The method for rapidly detecting the metal content in the urea aqueous solution of the nitrogen oxide reducing agent according to claim 1, wherein the mass-volume ratio of EDTA-2Na, 12-crown ether-4, auxiliary complexing agent, chrome black T, glycerol, triethanolamine, polyethylene glycol 8000, glucose, absolute ethyl alcohol and deionized water in the preparation detection solution is 7.5-8g:1-1.2mL:8-9g:3-3.5g:3-4mL:4-5mL:2.5-3g:2-3g:100-120mL:900-950mL.
7. The method for rapid detection of metal content in urea aqueous solution of nitrogen oxide reducing agent according to claim 1, wherein in the detection, ph=10 of the ammonia-ammonium chloride buffer solution;
the volume ratio of the urea for the vehicle to be tested to the ammonia water-ammonium chloride buffer solution is 100:3-5;
every 100mL of urea for the vehicle to be tested is dripped with 6-7 drops of detection liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410057765.2A CN117589759B (en) | 2024-01-16 | 2024-01-16 | Method for rapidly detecting metal content in urea aqueous solution of nitrogen oxide reducing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410057765.2A CN117589759B (en) | 2024-01-16 | 2024-01-16 | Method for rapidly detecting metal content in urea aqueous solution of nitrogen oxide reducing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117589759A CN117589759A (en) | 2024-02-23 |
| CN117589759B true CN117589759B (en) | 2024-03-26 |
Family
ID=89910176
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410057765.2A Active CN117589759B (en) | 2024-01-16 | 2024-01-16 | Method for rapidly detecting metal content in urea aqueous solution of nitrogen oxide reducing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117589759B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102614850A (en) * | 2012-04-04 | 2012-08-01 | 浙江工商大学 | Method for preparing crosslinked chitosan microsphere heavy metal ion adsorbent |
| CN110339818A (en) * | 2019-03-13 | 2019-10-18 | 广西中连智浩科技有限公司 | A kind of preparation method of modified magnetic chitosan absorbent |
| CN111545172A (en) * | 2020-05-11 | 2020-08-18 | 清华大学 | Supported adsorbent and preparation method and application thereof |
| CN112741847A (en) * | 2021-02-09 | 2021-05-04 | 浙江工业大学 | Method for removing heavy metals in Chinese herbal medicine materials by using plant polyphenol fatty acid ester |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9193899B2 (en) * | 2012-04-12 | 2015-11-24 | Halliburton Energy Services, Inc. | Treatment fluids comprising an alkali metal complexing agent and methods for use thereof |
-
2024
- 2024-01-16 CN CN202410057765.2A patent/CN117589759B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102614850A (en) * | 2012-04-04 | 2012-08-01 | 浙江工商大学 | Method for preparing crosslinked chitosan microsphere heavy metal ion adsorbent |
| CN110339818A (en) * | 2019-03-13 | 2019-10-18 | 广西中连智浩科技有限公司 | A kind of preparation method of modified magnetic chitosan absorbent |
| CN111545172A (en) * | 2020-05-11 | 2020-08-18 | 清华大学 | Supported adsorbent and preparation method and application thereof |
| CN112741847A (en) * | 2021-02-09 | 2021-05-04 | 浙江工业大学 | Method for removing heavy metals in Chinese herbal medicine materials by using plant polyphenol fatty acid ester |
Non-Patent Citations (3)
| Title |
|---|
| Eveliina Repo,et al.Adsorption of Co(II) and Ni(II) by EDTA- and/or DTPA-modified chitosan: Kinetic and equilibrium modeling.Chemical Engineering Journal.2010,第73-82页. * |
| Kumiko Ohtsu,et al.Complexation of Sodium, Potassium, Rubidium, Cesium and Ammonium Ions with 12-Crown-4 in N,N-Dimethylformamide and Water.Analytical Sciences.1996,第37-42页. * |
| 单宁酸基重金属吸附剂的制备及吸附性能研究;蒋沈益;万方学位论文;20230401;第9-16页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117589759A (en) | 2024-02-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN117589759B (en) | Method for rapidly detecting metal content in urea aqueous solution of nitrogen oxide reducing agent | |
| CN112209422B (en) | Method for preparing cerium oxide nanospheres | |
| CN106745151A (en) | Waste acid containing the zinc comprehensive treatment utilization method high | |
| CN101600809A (en) | The slurry preparation that use contains FeNi is used for the method for the raw material of stainless steel melt | |
| CN105879874A (en) | High-dispersion loaded nickel catalyst and preparation method thereof | |
| CN112047379A (en) | Method for precipitating ammonium polyvanadate | |
| CN110559856A (en) | vehicle urea and preparation method thereof | |
| CN109894004A (en) | A kind of urea for vehicle formula | |
| CN109985663B (en) | Method for post-treating Cu-SSZ-13 molecular sieve synthesized in situ by one-pot method | |
| CN206016924U (en) | Vehicle-mounted urea solution preparing device | |
| CN111348679A (en) | Preparation method of titanium dioxide powder for diesel vehicle tail gas denitration catalyst | |
| CN102452677B (en) | Treatment method for waste catalytic cracking catalyst | |
| CN115261086B (en) | Preparation method of blast furnace gas defluorination and decyanation purifying agent | |
| CN111805085A (en) | Method for improving welding performance of aluminum alloy sheet component of mountain bike | |
| CN115999362A (en) | Production process of urea solution for vehicles | |
| CN103055861A (en) | Copper catalyst and preparation method and application thereof | |
| CN114558622B (en) | Desulfurization catalyst for cooperatively removing hydrogen sulfide and carbonyl sulfide and preparation method thereof | |
| CN105622518B (en) | A kind of preparation method of 1H- imidazoles -4- formic acid | |
| CN103055867A (en) | Nickel catalyst and preparation method and application thereof | |
| CN114307641A (en) | High-purity solid automobile urea and preparation method thereof | |
| CN218371769U (en) | Titanium white metatitanic acid bleaching system | |
| CN108467443B (en) | Novel linear low-density polyethylene for urea box and preparation method thereof | |
| CN105085167A (en) | Two-section method process for preparing alcohol by oxalic ester hydrogenation | |
| CN113337715B (en) | Method for recycling vanadium and chromium from vanadium and chromium-containing wastewater | |
| CN118126217B (en) | Preparation method of chlorinated polyethylene wax |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |