CN114074113B - Clay mineral loaded chelated nano zero-valent iron and preparation method and application thereof - Google Patents
Clay mineral loaded chelated nano zero-valent iron and preparation method and application thereof Download PDFInfo
- Publication number
- CN114074113B CN114074113B CN202111335571.7A CN202111335571A CN114074113B CN 114074113 B CN114074113 B CN 114074113B CN 202111335571 A CN202111335571 A CN 202111335571A CN 114074113 B CN114074113 B CN 114074113B
- Authority
- CN
- China
- Prior art keywords
- clay mineral
- valent iron
- nano zero
- loaded
- chelated
- 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 239000002734 clay mineral Substances 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 28
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 26
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 16
- 239000011593 sulfur Substances 0.000 claims abstract description 16
- 229960000892 attapulgite Drugs 0.000 claims abstract description 13
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 7
- NYVOYAFUSJONHU-UHFFFAOYSA-K trisodium;1,3,5-triazine-2,4,6-trithiolate Chemical compound [Na+].[Na+].[Na+].[S-]C1=NC([S-])=NC([S-])=N1 NYVOYAFUSJONHU-UHFFFAOYSA-K 0.000 claims abstract description 7
- -1 iron ions Chemical class 0.000 claims abstract description 5
- 239000002689 soil Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 27
- 239000002351 wastewater Substances 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 13
- 229960002089 ferrous chloride Drugs 0.000 claims description 12
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 8
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052742 iron Inorganic materials 0.000 abstract description 5
- 238000005067 remediation Methods 0.000 abstract description 4
- 239000013522 chelant Substances 0.000 abstract 1
- 239000011651 chromium Substances 0.000 description 25
- 239000000463 material Substances 0.000 description 25
- 239000002245 particle Substances 0.000 description 19
- 229910021642 ultra pure water Inorganic materials 0.000 description 12
- 239000012498 ultrapure water Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 8
- 238000005054 agglomeration Methods 0.000 description 7
- 230000002776 aggregation Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000000634 powder X-ray diffraction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- WZRRRFSJFQTGGB-UHFFFAOYSA-N 1,3,5-triazinane-2,4,6-trithione Chemical compound S=C1NC(=S)NC(=S)N1 WZRRRFSJFQTGGB-UHFFFAOYSA-N 0.000 description 3
- 230000009920 chelation Effects 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical group C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002265 electronic spectrum Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 238000003895 groundwater pollution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000003802 soil pollutant Substances 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Soil Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses clay mineral loaded chelated nano zero-valent iron and a preparation method and application thereof, and belongs to the technical field of heavy metal pollution remediation. The method is characterized in that nitrogen-containing or sulfur-containing compounds including N, N-dimethylformamide and trimercapto-s-triazine trisodium salt are adopted to chelate divalent iron ions, then the obtained mixture is mixed with clay mineral attapulgite, sodium borohydride is added to reduce the mixture into chelated nano zero-valent iron, and finally the clay mineral loaded chelated nano zero-valent iron is formed.
Description
Technical Field
The invention belongs to a heavy metal pollution remediation technology, and relates to clay mineral loaded chelated nano zero-valent iron and a preparation method and application thereof.
Background
Heavy metal means a density of greater than 5.0g/cm 3 The metal and excessive heavy metal enter the environment to reduce the quality of atmosphere, water and soil, the heavy metal pollution has concealment, persistence and irreversible property, is difficult to degrade in the environment, can be continuously amplified and accumulated in certain organs of organisms through direct inhalation, ingestion and skin contact, and the obvious biological toxicity seriously threatens the health of animals and human beings. Heavy metal pollution is spread all over the world, china is one of the biggest metal producing and consuming countries in the world, and with the rapid development of social economy in the past decades, the serious heavy metal pollution problem gradually spreads nationwide, wherein the chromium (Cr) and cadmium (Cd) elements are the most serious. The existing form of Cr in water and soil mainly has two valence states: cr (III) and Cr (VI), wherein Cr (VI) is a carcinogen and is about 100 times more toxic than Cr (III). Heavy metals in soil can permeate underground along with the lapse of time, cause groundwater pollution, finally flow into animals and plants, threaten human existence and development.
The technology for repairing heavy metal pollution mainly comprises a physical method, a chemical method and a biological method. Although research has been carried out for many years, the defects of large dosage of the medicament, high cost, low efficiency, short durability, weak applicability to actual polluted water and soil and the like exist in the repairing process. The nanometer zero-valent iron in-situ reduction repairing technology belongs to the category of in-situ chemical reduction methods, is a technology for repairing heavy metal pollution with great development prospect, and has the following advantages: (1) The polluted water body or soil does not need to be transported remotely, so that a large amount of transportation cost is saved; (2) The construction cost is low, and expensive engineering facilities and equipment do not need to be built generally; (3) the operation and maintenance are relatively simple; (4) The soil layer is not stirred, the original appearance of the soil layer is not damaged, and the method is suitable for a field developed and utilized in the later period; (5) Can realize the restoration of deep soil and underground water, and is suitable for large-scale restoration engineering.
Essentially, the iron reduction method belongs to the category of chemical remediation. Fe can be Fe in nature 0 、Fe 2+ 、Fe 3+ Three valence states exist. In general, 0-valent Fe is unstable. Fe 0 Is very easy to be oxidized into Fe 2+ . In a water/soil system, the half-cell reaction involving Fe (II)/Fe 0 is:
Fe 2+ +2→Fe 0 （E 0 Fe(II)/Fe(0) =-0.44V）
as can be seen from the chemical thermodynamics and the chemical reaction kinetics, fe is generated due to the negative Eh of the above reaction 2+ Conversion to Fe 0 Is not easy. However, once Fe is artificially synthesized 0 And is smoothly transported to a contaminated target site, and the strong reducibility thereof becomes an advantage. Fe 0 Is easy to be oxidized, and the heavy metal ions in the polluted target are easy to obtain Fe 0 The electrons are reduced, thereby achieving the aim of repairing soil pollutants.
At present, the granularity of nano zero-valent iron prepared at home and abroad is within the range of 12nm to 120nm. In general, the smaller the particle size, the more the surface of the active component Fe is exposed, and the larger the contact surface with the contaminant, the better the effect of repairing the contaminant. Meanwhile, there are some problems, such as the smaller the particle size, the stronger the reactivity, the easier the nano zero-valent iron is to deactivate, and the processing cost is increased accordingly. The difference of the nanometer zero-valent iron particle size can affect the reaction rate and the reaction capacity of the reduction reaction with the heavy metal. The common nano iron powder has active properties, is easy to oxidize or agglomerate, has the influence of earth magnetic field and the static magnetic force among particles, is called soft agglomeration due to physical bonding, is called hard agglomeration due to chemical bonding, is difficult to open chemical agglomeration, and needs to stabilize the particles and avoid agglomeration at each step of the preparation stage, the storage stage and the use stage in order to destroy the agglomeration of nano iron particles.
The existing dispersion technology is realized by adding a proper stabilizer, the adopted stabilizer is mostly a surfactant, such as carboxymethyl cellulose, uronic acid and the like, and the practical application of zero-valent iron in pollution remediation is restricted due to high economic cost. Therefore, the search for an economical, cheap, efficient and stable nano-iron preparation method with good compatibility with soil is one of the key scientific and technological problems which need to be solved at present.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide clay mineral loaded chelated nano zero-valent iron and a preparation method and application thereof, which are used for removing heavy metal ions in water or soil and solve the problems of easy agglomeration, high cost and low capability of removing heavy metal ions of common zero-valent iron.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a preparation method of clay mineral loaded chelated nano zero-valent iron, which comprises the following steps:
1) Adding clay mineral, ferrous chloride and nitrogen-containing or sulfur-containing compound into water, and stirring until the mixture is uniformly mixed to obtain a mixed solution;
2) And (3) dripping the prepared sodium borohydride solution into the mixed solution, carrying out solid-liquid separation after full reaction, and then cleaning and drying the solid to obtain the clay mineral supported chelated nano zero-valent iron.
Further, in the step 1), the clay mineral is attapulgite, and the nitrogen-containing or sulfur-containing compound is one or a combination of two of N, N-dimethylformamide and trimercapto-s-triazine trisodium salt; the stirring time is 5min to 10min.
Further, in the step 1), when the nitrogen-containing or sulfur-containing compound is N, N-dimethylformamide, the ratio of the clay mineral, ferrous chloride, the nitrogen-containing or sulfur-containing compound and water is (1 to 1.2) g: (3.5 to 4) g: (4 to 4.5) mL: (300 to 500) mL.
Further, when the nitrogen-containing or sulfur-containing compound is trimercapto-s-triazine trisodium salt, the using amount ratio of the clay mineral, the ferrous chloride to the nitrogen-containing or sulfur-containing compound to the water is (1 to 1.5) g: (5 to 5.5) g: (2 to 3) g: (300 to 500) mL.
Further, in the step 2), when preparing the sodium borohydride solution, the dosage ratio of the sodium borohydride to the water is (4 to 5) g, (75 to 100) mL.
Further, in the step 2), the using amount proportion range of the sodium borohydride solution and the mixed solution is (4 to 5) g, (75 to 100) mL; the reaction time is from 20min to 30min.
Further, vacuum freeze drying is carried out at-60 ℃ to-50 ℃.
The invention also discloses the clay mineral loaded chelated nano zero-valent iron prepared by the preparation method of the clay mineral loaded chelated nano zero-valent iron.
The invention also discloses application of the clay mineral loaded chelated nano zero-valent iron as a heavy metal remover in water or soil.
Further, the clay mineral loaded chelated nano zero-valent iron is applied to the removal of heavy metals in Cr (VI) -containing wastewater with the concentration of 1 to 100mg/L, cd (II) -containing contaminated soil with the concentration of 1 to 50mg/kg and Cr (VI) -containing contaminated soil with the concentration of 1 to 200mg/kg.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of clay mineral loaded chelated nano zero-valent iron 4 The solution is added into the mixed solution to form the clay mineral loaded chelated nano zero-valent iron heavy metal ion remover. The clay mineral used in the invention is attapulgite, the source is wide, the price is low, compared with the clay mineral loaded zero-valent iron formed without adding nitrogen or sulfur-containing compounds, the prepared clay mineral loaded chelated nano zero-valent iron material has higher removal efficiency, has good removal capacity for heavy metal ions, overcomes the defect of low removal capacity of the zero-valent iron material for the heavy metal ions, increases the possibility of applying the composite material to actual heavy metal ion wastewater or polluted soil, and has very wide application prospect in the aspect of treating water or soil pollution.
Furthermore, the invention selects a nitrogen-containing or sulfur-containing compound which has stronger chelation on ferrous ions, and then adds a reducing agent NaBH 4 And (2) obtaining a clay mineral loaded chelated nano zero-valent iron, wherein the obtained chelated nano zero-valent iron is amorphous zero-valent iron, the amorphous state has higher energy than the crystalline phase of the same component, and is in an energetically unstable state, and the work function (4.349 eV) of the clay mineral loaded chelated nano zero-valent iron is lower than that of the clay mineral loaded nano zero-valent iron (4.436 eV) through an ultraviolet light electronic spectrum (UPS) test, so that the clay mineral loaded chelated nano zero-valent iron has a faster electron transfer rate and a lower electron transfer resistance, and therefore, the clay mineral loaded chelated nano zero-valent iron has a higher removal efficiency, and an ideal effect of removing heavy metal ions in water or soil is achieved.
The invention also discloses the clay mineral loaded chelated nano zero-valent iron prepared by the preparation method of the clay mineral loaded chelated nano zero-valent iron and a water or soil heavy metal remover prepared by the clay mineral loaded chelated nano zero-valent iron. According to the related experiment results, when the reaction time is 30min, the removal rates of the simulated Cr (VI) wastewater and Cd (II) wastewater with the initial concentration of 20mg/L reach 100%, the removal rates of the simulated Cr (VI) wastewater and Cd (II) wastewater with the initial concentration of 75mg/L are 81.4% and 87.6% respectively, and even if the removal rates of the simulated Cr (VI) wastewater and Cd (II) wastewater with the initial concentration of 100mg/L are 70.7% and 80.9% respectively; in the application of the material in soil, after the reaction is carried out for 30 minutes, the removal rate of simulated Cr (VI) polluted soil with the initial concentration of 75mg/kg is 98.6 percent, the removal rate of simulated Cr (VI) polluted soil with the initial concentration of 200mg/kg is 84.1 percent, the removal rate of simulated Cd (II) polluted soil with the initial concentration of 15mg/kg is 93.5 percent, the removal rate of simulated Cd (II) polluted soil with the initial concentration of 50mg/kg is 75.8 percent, and the removal rates of all the materials are obviously superior to those of clay mineral loaded nano zero-valent iron materials.
Drawings
FIG. 1 is a real object diagram of the clay mineral supported chelated nano zero-valent iron material prepared in examples 1 to 3;
wherein: a, adding N, N-dimethylformamide to form clay mineral loaded chelated nano zero-valent iron; b-adding the trithiol-s-triazine trisodium salt to form clay mineral loaded chelated nano zero-valent iron;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the clay mineral supported chelated nano zero-valent iron material prepared in examples 1 to 3;
wherein: a, adding N, N-dimethylformamide to form clay mineral loaded chelated nano zero-valent iron; b-adding the trithiol-s-triazine trisodium salt to form clay mineral loaded chelated nano zero-valent iron;
FIG. 3 is a comparison graph of X-ray powder diffraction (XRD) of the chelated nanoscale zero-valent iron supported by the clay minerals prepared in examples 1 to 3 and the nanoscale zero-valent iron supported by the clay mineral prepared in comparative example 1;
wherein: a-adding N, N-dimethylformamide to form clay mineral loaded chelated nano zero-valent iron and the clay mineral loaded nano zero-valent iron prepared in the comparative example 1; b-adding the trithiol-s-triazine trisodium salt to form the clay mineral loaded chelated nano zero-valent iron and the clay mineral loaded nano zero-valent iron prepared in the comparative example 1;
FIG. 4 is a graph comparing ultraviolet light electron function (UPS) of chelated nano zero-valent iron supported by clay mineral and nano zero-valent iron supported by clay mineral;
FIG. 5 is a comparison graph of the clay mineral loaded chelated nano zero-valent iron material prepared in examples 1 to 3 and the clay mineral loaded nano zero-valent iron prepared in comparative example 1 for removing Cr (VI) and Cd (II) elements in water or soil;
wherein: a-the effect of removing Cr (VI) in the water body; b-removing effect on Cd (II) in the water body; c-effect of removing Cr (VI) from soil; d-removal effect on soil Cd (II).
Detailed Description
In order to make those skilled in the art better understand the technical solutions of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in other sequences than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the accompanying drawings:
example 1
A preparation method of clay mineral loaded chelated nano zero-valent iron comprises the following steps:
1) Under the condition of room temperature and normal pressure, 1.0000g of attapulgite, 3.5000g of ferrous chloride and 4mLN and N-dimethylformamide are added into a three-neck flask filled with 300mL of ultrapure water, and stirred for 5min to be uniformly mixed to obtain a mixed solution;
2) Adding 4.0000g of sodium borohydride and 75mL of ultrapure water into a 100mL beaker, and stirring for dissolving to obtain a sodium borohydride solution; dropwise adding the obtained sodium borohydride solution into the mixed solution obtained in the step 1), gradually forming particles in the solution, fully reacting for 20 minutes after dropwise adding, separating solid particles by using a magnet, washing with water, and performing vacuum freeze drying at-60 ℃ to obtain the clay mineral supported chelated nano zero-valent iron.
Example 2
A preparation method of clay mineral loaded chelated nano zero-valent iron comprises the following steps:
1) Under the conditions of room temperature and normal pressure, 1.1000g of attapulgite, 3.7000g of ferrous chloride, 4.2mLN and N-dimethylformamide are added into a three-neck flask filled with 350mL of ultrapure water and stirred for 7min to be uniformly mixed to obtain a mixed solution;
2) Adding 4.5000g of sodium borohydride and 80mL of ultrapure water into a 100mL beaker, and stirring for dissolving to obtain a sodium borohydride solution; dropwise adding the obtained sodium borohydride solution into the mixed solution obtained in the step 1), gradually forming particles in the solution, fully reacting for 25 minutes after dropwise adding, separating solid particles by using a magnet, washing with water, and performing vacuum freeze drying at-55 ℃ to obtain the clay mineral supported chelated nano zero-valent iron.
Example 3
A preparation method of clay mineral loaded chelated nano zero-valent iron comprises the following steps:
1) Under the conditions of room temperature and normal pressure, 1.2000g of attapulgite, 4.0000g of ferrous chloride and 4.5mLN and N-dimethylformamide are added into a three-neck flask filled with 500mL of ultrapure water and stirred for 10min to be uniformly mixed to obtain a mixed solution;
2) Adding 5.0000g of sodium borohydride and 100mL of ultrapure water into a 100mL beaker, and stirring for dissolving to obtain a sodium borohydride solution; dropwise adding the obtained sodium borohydride solution into the mixed solution obtained in the step 1), gradually forming particles in the solution, fully reacting for 30 minutes after dropwise adding, separating solid particles by using a magnet, washing with water, and performing vacuum freeze drying at-60 ℃ to obtain the clay mineral supported chelated nano zero-valent iron.
Example 4
A preparation method of clay mineral loaded chelated nano zero-valent iron comprises the following steps:
1) Under the condition of room temperature and normal pressure, adding 1.0000g of attapulgite, 5.0000g of ferrous chloride and 2.0000 g of trimercapto-s-triazine trisodium salt into a three-neck flask filled with 300mL of ultrapure water, and stirring for 5min to uniformly mix the materials to obtain a mixed solution;
2) Adding 4.0000g of sodium borohydride and 75mL of ultrapure water into a 100mL beaker, and stirring for dissolving to obtain a sodium borohydride solution; dropwise adding the obtained sodium borohydride solution into the mixed solution obtained in the step 1), gradually forming particles in the solution, fully reacting for 20 minutes after dropwise adding is completed, separating solid particles by using a magnet, washing by using water, and performing vacuum freeze drying at-50 ℃ to obtain the clay mineral loaded chelated nano zero-valent iron.
Example 5
A preparation method of clay mineral loaded chelated nano zero-valent iron comprises the following steps:
1) Under the condition of room temperature and normal pressure, adding 1.3000g of attapulgite, 5.3000 g of ferrous chloride and 2.5000g of trimercapto-s-triazine trisodium salt into a three-neck flask filled with 450mL of ultrapure water, and stirring for 8min to uniformly mix the materials to obtain a mixed solution;
2) Adding 4.7000g of sodium borohydride and 90mL of ultrapure water into a 100mL beaker, and stirring for dissolving to obtain a sodium borohydride solution; dropwise adding the obtained sodium borohydride solution into the mixed solution obtained in the step 1), gradually forming particles in the solution, fully reacting for 25 minutes after dropwise adding, separating solid particles by using a magnet, washing with water, and performing vacuum freeze drying at-55 ℃ to obtain the clay mineral loaded chelated nano zero-valent iron.
Example 6
A preparation method of clay mineral loaded chelated nano zero-valent iron comprises the following steps:
1) Under the condition of room temperature and normal pressure, adding 1.5000g of attapulgite, 5.5000g of ferrous chloride and 3.0000g of trimercapto-s-triazine trisodium salt into a three-neck flask filled with 500mL of ultrapure water, and stirring for 10min to uniformly mix to obtain a mixed solution;
2) Adding 5.0000g of sodium borohydride and 100mL of ultrapure water into a 100mL beaker, and stirring for dissolving to obtain a sodium borohydride solution; dropwise adding the obtained sodium borohydride solution into the mixed solution obtained in the step 1), gradually forming particles in the solution, fully reacting for 30 minutes after dropwise adding, separating solid particles by using a magnet, washing with water, and performing vacuum freeze drying at-60 ℃ to obtain the clay mineral supported chelated nano zero-valent iron.
Comparative example 1
The preparation method of the clay mineral loaded nano zero-valent iron material is carried out according to the preparation method of the clay mineral loaded chelated nano zero-valent iron in the embodiments 1 to 6, but no nitrogen or sulfur-containing compound is added.
Fig. 1 is a real object diagram of a clay mineral supported chelated nano zero-valent iron material, and it is seen from the diagram that under the influence of a nitrogen-containing or sulfur-containing compound, two synthesized zero-valent iron supported materials are slightly different in color, which may be that different chelation strengths of the nitrogen-containing or sulfur-containing compound cause different particle sizes, which affect the diffuse reflection of visible light to cause color differences, but the two substances are still in a fine powder state, which is beneficial to the adsorption of pollutants.
FIG. 2 is a Scanning Electron Microscope (SEM) image of a clay mineral loaded chelated nano zero-valent iron material; as can be seen from the SEM image, a plurality of rod-shaped structures are arranged around the zero-valent iron, which is a remarkable characteristic of the attapulgite, and the larger specific surface area of the attapulgite provides ideal support for the zero-valent iron. After loading, the agglomeration effect of the two kinds of zero-valent iron is well relieved,
fig. 3 shows a comparison diagram of X-ray powder diffraction (XRD) of the clay mineral supported chelated nano zero-valent iron and the clay mineral supported nano zero-valent iron prepared by the present invention, wherein the diagrams (a and b) show that 8.42 °, 13.62 °, 20.78 ° and 26.64 ° correspond to characteristic diffraction peaks of attapulgite, and all clay mineral supported chelated nano zero-valent iron composite materials do not have crystallization peaks at 44.8 ° compared with the clay mineral supported nano zero-valent iron material, and the peaks at 44.8 ° are classified as significant crystallization peaks of zero-valent iron, which indicates that chelation of the selected nitrogen or sulfur-containing compound to divalent iron ions makes the zero-valent iron formed in the reduction process in an amorphous state, which is higher in crystalline phase energy than the same component thereof, and is in an energy unstable state, and amorphous zero-valent iron is more likely to donate electrons. X-ray powder diffraction (XRD) of the chelated nanoscale zero-valent iron loaded on the clay mineral indicates that the chelated nanoscale zero-valent iron is successfully loaded on the clay mineral.
Fig. 4 is a comparison graph of ultraviolet light electron function (UPS) of the clay mineral loaded chelated nano zero-valent iron and the clay mineral loaded nano zero-valent iron prepared by the present invention, the work functions of the clay mineral loaded chelated nano zero-valent iron and the clay mineral loaded nano zero-valent iron calculated by the UPS are 4.349eV and 4.436eV, respectively, the magnitude of the work function indicates the strength of the constraint of electrons in the metal, and the larger the work function is, the less the electrons are easy to leave the metal. A low work function has a lower energy barrier and is more prone to provide electrons from the material surface to the target contaminant. The result shows that the clay mineral loaded chelated nano zero-valent iron is easier to donate electrons and has faster reaction rate with pollutants.
Application example 1
0.05g of the materials prepared in examples 1 to 3 and comparative example 1 was weighed and charged into a 250mL Erlenmeyer flask. Respectively taking 50mL of heavy metal Cr (VI) wastewater with the concentrations of 5, 20, 50, 75 and 100mg/L, shaking at room temperature, reacting for 30min, and measuring the simulated heavy metal Cr (VI) wastewater by using a dibenzoyl dihydrazide spectrophotometer method (GB 7467-1987), wherein the comparison result is shown in figure 5-a.
Application example 2
0.05g of the materials prepared in examples 1 to 3 and comparative example 1 was weighed and charged into a 250mL Erlenmeyer flask. Respectively taking 50mL of heavy metal Cd (II) wastewater with the concentrations of 5, 20, 50, 75 and 100mg/L, oscillating at room temperature, reacting for 30 minutes, and measuring the simulated heavy metal Cd (II) wastewater by using an inductively coupled plasma emission spectrometer (ICP-OES), wherein the comparison result is shown in figure 5-b.
Application example 3
Respectively weighing 10.000g of Cr (VI) polluted soil added with standard 1mg/kg, 20mg/kg, 75mg/kg, 150mg/kg and 200mg/kg into a 250mL conical flask, adding 100mL of distilled water, respectively adding 0.1g of the materials prepared in the examples 1 to 3 and the comparative example 1, oscillating at room temperature, reacting for 30 minutes, respectively taking out samples, filtering, and measuring the concentration of Cr (VI) in the solution by adopting a dibenzoyl dihydrazide spectrophotometry method, wherein the comparison result is shown in a graph 5-c.
Application example 4
Respectively weighing 10.000g of Cd (II) contaminated soil added with standard 1mg/kg, 15mg/kg, 25mg/kg, 35mg/kg and 50mg/kg into a 250mL conical flask, adding 100mL of distilled water, adding 0.1g of the materials prepared in examples 1 to 3 and comparative example 1, oscillating at room temperature, reacting for 30 minutes, respectively taking out samples, filtering, and adopting an inductively coupled plasma emission spectrometer (ICP-OES), wherein the comparison result is shown in FIG. 5-d.
As can be seen from FIG. 5, the removal rate of the clay mineral loaded chelated nano zero-valent iron material is significantly better than that of the clay mineral loaded nano zero-valent iron material. After reacting for 30 minutes, the removal rates of the simulated Cr (VI) wastewater and Cd (II) wastewater with the initial concentration of 20mg/L reach 100 percent, the removal rates of the simulated Cr (VI) wastewater and Cd (II) wastewater with the initial concentration of 75mg/L are 81.4 percent and 87.6 percent respectively, and even if the simulated Cr (VI) wastewater and Cd (II) wastewater with the initial concentration of 100mg/L are 70.7 percent and 80.9 percent respectively; in the application of the material in soil, after the reaction is carried out for 30 minutes, the removal rate of simulated Cr (VI) polluted soil with the initial concentration of 75mg/kg is 98.6 percent, the removal rate of simulated Cr (VI) polluted soil with the initial concentration of 200mg/kg is 84.1 percent, the removal rate of simulated Cd (II) polluted soil with the initial concentration of 15mg/kg is 93.5 percent, the removal rate of simulated Cd (II) polluted soil with the initial concentration of 50mg/kg is 75.8 percent, and the removal rates of all the materials are obviously superior to those of clay mineral loaded nano zero-valent iron materials.
The above contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention should not be limited thereby, and any modification made on the basis of the technical idea proposed by the present invention falls within the protection scope of the claims of the present invention.
Claims (7)
1. A preparation method of clay mineral loaded chelated nano zero-valent iron is characterized by comprising the following steps:
1) Adding clay mineral, ferrous chloride and nitrogen-containing compound or sulfur-containing compound into water, and stirring until the mixture is uniformly mixed to obtain a mixed solution;
when the nitrogen-containing compound is N, N-dimethylformamide, the dosage ratio of the clay mineral, ferrous chloride, the nitrogen-containing compound and water is (1 to 1.2) g: (3.5 to 4) g: (4 to 4.5) mL: (300-500) mL;
when the sulfur-containing compound is trimercapto-s-triazine trisodium salt, the using amount ratio of the clay mineral, the ferrous chloride, the sulfur-containing compound and the water is (1 to 1.5) g: (5 to 5.5) g: (2 to 3) g: (300 to 500) mL;
the clay mineral is attapulgite; stirring for 5min to 10min;
2) And (3) dripping the prepared sodium borohydride solution into the mixed solution, carrying out solid-liquid separation after full reaction, and then cleaning and drying the solid to obtain the clay mineral loaded chelated nano zero-valent iron.
2. The preparation method of the clay mineral supported chelated nano zero-valent iron as claimed in claim 1, wherein in the step 2), when a sodium borohydride solution is prepared, the usage ratio of sodium borohydride to water is (4 to 5) g, (75 to 100) mL.
3. The method for preparing the clay mineral loaded chelated nano zero-valent iron as claimed in claim 1, wherein in step 2), the reaction time is from 20min to 30min.
4. The preparation method of the clay mineral supported chelated nano zero-valent iron according to claim 1, wherein in the step 2), the drying is vacuum freeze drying, and is performed at-60 ℃ to-50 ℃.
5. The clay mineral loaded chelated nano zero-valent iron prepared by the preparation method of the clay mineral loaded chelated nano zero-valent iron according to any one of claims 1 to 4.
6. The use of the clay mineral-loaded chelated nano zero-valent iron of claim 5 as a heavy metal remover in water or soil.
7. The application of the clay mineral-loaded chelated nano zero-valent iron disclosed in claim 5 in removing heavy metals in Cr (VI) -containing wastewater with a concentration of 1-100mg/L, cd (II) -containing contaminated soil with a concentration of 1-50mg/kg and Cr (VI) -containing contaminated soil with a concentration of 1-200mg/kg.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111335571.7A CN114074113B (en) | 2021-11-11 | 2021-11-11 | Clay mineral loaded chelated nano zero-valent iron and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111335571.7A CN114074113B (en) | 2021-11-11 | 2021-11-11 | Clay mineral loaded chelated nano zero-valent iron and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114074113A CN114074113A (en) | 2022-02-22 |
| CN114074113B true CN114074113B (en) | 2022-10-25 |
Family
ID=80283710
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111335571.7A Active CN114074113B (en) | 2021-11-11 | 2021-11-11 | Clay mineral loaded chelated nano zero-valent iron and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114074113B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114751502B (en) * | 2022-03-24 | 2023-06-23 | 陕西省中勘环境地质研究中心有限公司 | Core-shell structure modified nano zero-valent iron and preparation method and application thereof |
| CN114682222B (en) * | 2022-06-01 | 2022-08-16 | 矿冶科技集团有限公司 | Adsorption material for treating wastewater containing arsenic, antimony and molybdenum, preparation method thereof and method for treating wastewater containing arsenic, antimony and molybdenum by using adsorption material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105363773A (en) * | 2015-12-08 | 2016-03-02 | 湖南康盟环保科技有限公司 | Heavy metal fixing agent and in-situ repair method for heavy metal contaminated soil |
| CN106984640A (en) * | 2017-05-08 | 2017-07-28 | 湖南大学 | The method of nano zero valence iron restoration of soil polluted by heavy metal |
| CN108048096A (en) * | 2017-12-15 | 2018-05-18 | 云南圣清环保科技有限公司 | One kind is used for containing Cr（Ⅵ）Magnetic green substance new material stabilizer of soil treatment and preparation method thereof |
| CN110342626A (en) * | 2019-06-21 | 2019-10-18 | 湖南省烟草公司长沙市公司 | A kind of clay mineral load nano zero valence iron and its preparation method and application |
| CN111019663A (en) * | 2019-12-24 | 2020-04-17 | 甘肃瀚兴环保科技有限公司 | Heavy metal passivation material of nano zero-valent iron composite attapulgite, preparation method and application thereof |
-
2021
- 2021-11-11 CN CN202111335571.7A patent/CN114074113B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105363773A (en) * | 2015-12-08 | 2016-03-02 | 湖南康盟环保科技有限公司 | Heavy metal fixing agent and in-situ repair method for heavy metal contaminated soil |
| CN106984640A (en) * | 2017-05-08 | 2017-07-28 | 湖南大学 | The method of nano zero valence iron restoration of soil polluted by heavy metal |
| CN108048096A (en) * | 2017-12-15 | 2018-05-18 | 云南圣清环保科技有限公司 | One kind is used for containing Cr（Ⅵ）Magnetic green substance new material stabilizer of soil treatment and preparation method thereof |
| CN110342626A (en) * | 2019-06-21 | 2019-10-18 | 湖南省烟草公司长沙市公司 | A kind of clay mineral load nano zero valence iron and its preparation method and application |
| CN111019663A (en) * | 2019-12-24 | 2020-04-17 | 甘肃瀚兴环保科技有限公司 | Heavy metal passivation material of nano zero-valent iron composite attapulgite, preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Amorphization enables highly efficient anaerobic thiamphenicol reduction by zero-valent iron;Shen WJ et al.;《Applied Catalysis B: Environmental》;https://www.webofscience.com/wos/alldb/full-record/WOS:000515195200064;20200505;第264卷;文献号118550 * |
| 有机凹凸棒石负载纳米零价铁去除水中六价铬;徐海玉等;《中国环境科学》;20191220;第39卷(第12期);第5079~5084页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114074113A (en) | 2022-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | In-situ remediation of hexavalent chromium contaminated groundwater and saturated soil using stabilized iron sulfide nanoparticles | |
| Sun et al. | Aqueous Hg (II) immobilization by chitosan stabilized magnetic iron sulfide nanoparticles | |
| Meng et al. | Treatment of arsenic in Bangladesh well water using a household co-precipitation and filtration system | |
| CN114074113B (en) | Clay mineral loaded chelated nano zero-valent iron and preparation method and application thereof | |
| Dries et al. | Effect of humic acids on heavy metal removal by zero-valent iron in batch and continuous flow column systems | |
| Tokunaga et al. | Acid washing and stabilization of an artificial arsenic-contaminated soil | |
| Hou et al. | Simultaneous reduction and immobilization of Cr (VI) in seasonally frozen areas: Remediation mechanisms and the role of ageing | |
| Danila et al. | Immobilisation of metal (loid) s in two contaminated soils using micro and nano zerovalent iron particles: Evaluating the long-term stability | |
| Polettini et al. | A kinetic study of chelant-assisted remediation of contaminated dredged sediment | |
| Wang et al. | Biological aqua crust mitigates metal (loid) pollution and the underlying immobilization mechanisms | |
| CN109762569B (en) | Heavy metal cadmium and arsenic composite contaminated soil remediation agent and preparation method thereof | |
| Gluhar et al. | The use of zero-valent Fe for curbing toxic emissions after EDTA-based washing of Pb, Zn and Cd contaminated calcareous and acidic soil | |
| Duan et al. | Zero valent iron or Fe3O4-loaded biochar for remediation of Pb contaminated sandy soil: Sequential extraction, magnetic separation, XAFS and ryegrass growth | |
| Li et al. | Potentiality of phosphorus− accumulating organisms biomasses in biosorption of Cd (II), Pb (II), Cu (II) and Zn (II) from aqueous solutions: Behaviors and mechanisms | |
| CN113233570A (en) | Preparation method of sodium bentonite loaded zero-valent iron and application of sodium bentonite loaded zero-valent iron in treatment of composite polluted underground water | |
| Xu et al. | Removal of heavy metal (loid) s from aqueous solution by biogenic FeS–kaolin composite: Behaviors and mechanisms | |
| Zhao et al. | Stabilized green rusts for aqueous Cr (VI) removal: Fast kinetics, high iron utilization rate and anti-acidification | |
| CN103170501A (en) | Preparation method of in-situ repair material for soil polluted by heavy metal chromium and application of material | |
| Wan et al. | Selective removal of total Cr from a complex water matrix by chitosan and biochar modified-FeS: Kinetics and underlying mechanisms | |
| Qu et al. | Improved performance and applicability of copper-iron bimetal by sulfidation for Cr (VI) removal | |
| Shen et al. | Study on the adsorption process of Cd (II) by Mn-diatomite modified adsorbent | |
| Li et al. | Reducing geogenic arsenic leaching from excavated sedimentary soil using zero-valent iron amendment followed by dry magnetic separation: A case study | |
| Xu et al. | Simultaneous and efficient removal of multiple heavy metal (loid) s from aqueous solutions using Fe/Mn (hydr) oxide and phosphate mineral composites synthesized by regulating the proportion of Fe (II), Fe (III), Mn (II) and PO43– | |
| Zhao et al. | One-time removal of Cr (VI) and carbon tetrachloride from groundwater by silicate stabilized green rust: the slow release of reactive sites driven by Fe (III)-Cr (III) oxides formation | |
| Zou et al. | Simultaneous removal of Cr (VI), Cd, and Pb from aqueous solution by iron sulfide nanoparticles: Influencing factors and interactions of metals |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231218 Address after: Room 1037, 1st Floor, JuGou Hongde Building, No. 20, West China Science and Technology Innovation Port, Fengxi New City, Xixian New District, Xi'an City, Shaanxi Province, 712046 Patentee after: Shaanxi Qingling Chunchuang Environmental Protection Industry Technology Co.,Ltd. Address before: 710049 No. 28 West Xianning Road, Shaanxi, Xi'an Patentee before: XI'AN JIAOTONG University |
|
| TR01 | Transfer of patent right |