CN111908816A - Method for photo-biomimetic catalytic oxidation of chloride ions and organic matters in sea sand - Google Patents
Method for photo-biomimetic catalytic oxidation of chloride ions and organic matters in sea sand Download PDFInfo
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- CN111908816A CN111908816A CN202010626696.4A CN202010626696A CN111908816A CN 111908816 A CN111908816 A CN 111908816A CN 202010626696 A CN202010626696 A CN 202010626696A CN 111908816 A CN111908816 A CN 111908816A
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- sea sand
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- chloride ions
- organic matters
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- 239000004576 sand Substances 0.000 title claims abstract description 86
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 34
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 34
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 31
- 230000003647 oxidation Effects 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 12
- 238000007664 blowing Methods 0.000 claims abstract description 11
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000005286 illumination Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 230000003592 biomimetic effect Effects 0.000 claims description 10
- 150000004032 porphyrins Chemical class 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 231100000053 low toxicity Toxicity 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000013505 freshwater Substances 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- KBTRJWUKQYZNGB-UHFFFAOYSA-N 3,5,7,21-tetraphenyl-23H-porphyrin-2-carboxylic acid Chemical compound C=1C=CC=CC=1N1C2=C(C=3C=CC=CC=3)C(C(=C3)C=4C=CC=CC=4)=NC3=CC(N3)=CC=C3C=C(N=3)C=CC=3C=C1C(C(=O)O)=C2C1=CC=CC=C1 KBTRJWUKQYZNGB-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- JQRLYSGCPHSLJI-UHFFFAOYSA-N [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JQRLYSGCPHSLJI-UHFFFAOYSA-N 0.000 description 1
- XJJWWOUJWDTXJC-UHFFFAOYSA-N [Mn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Mn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 XJJWWOUJWDTXJC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- OSVXSBDYLRYLIG-UHFFFAOYSA-N chlorine dioxide Inorganic materials O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 150000003278 haem Chemical class 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 tetraphenyl carboxyl iron porphyrin Chemical compound 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
- C04B20/023—Chemical treatment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
- C04B14/06—Quartz; Sand
- C04B14/068—Specific natural sands, e.g. sea -, beach -, dune - or desert sand
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Civil Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for photo-biomimetic catalytic oxidation of chloride ions and organic matters in sea sand, which comprises the following steps of (1): putting sea sand into a drum mixer, injecting water for mixing, and blowing air into the drum mixer; step (2): adding metalloporphyrin, a catalyst auxiliary agent and a photosensitizer into the roller in the step (1), continuously stirring and blowing air, and carrying out catalytic oxidation reaction at a certain temperature under a certain illumination condition; and (3): and (3) after the reaction in the step (2) is finished, carrying out solid-liquid separation on the sea sand and water, washing the sea sand by water, and drying to obtain the finished sand. The method has the advantages of simple operation flow, low cost, small dosage, safety, low toxicity, no secondary pollution and high selectivity, and can effectively remove chloride ions and organic matters in the sea sand.
Description
Technical Field
The invention relates to the field of sea sand purification, in particular to a method for oxidizing chloride ions and organic matters in sea sand by using photo-biomimetic catalysis.
Background
At present, China continuously tries to use sea sand to replace river sand, but in the process of using the sea sand, strict requirements on the content of chloride ions and other harmful substances are met. Therefore, the sea sand must be purified to meet the use standards specified by the specifications before being put into use.
At present, the method for purifying sea sand in China mainly comprises a natural placing method, a fresh water flushing method, a mechanical separation method and the like. The natural placement method is not suitable for building development in China due to long time consumption, other purification methods consume a large amount of fresh water resources, the efficiency of removing chloride ions and organic matters in sea sand is not high, resources are wasted, and the cost is increased. In the present day of the increasing shortage of fresh water resources, new sea sand purification methods either break away from fresh water dependence or increase the capital investment for wastewater treatment, and can effectively remove chloride ions and organic matters in sea sand. The existing method for removing chloride ions and organic matters in sea sand to purify the sea sand is not ideal.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a method for high-efficiently removing chloride ions and organic matters in sea sand by means of photo-biomimetic catalytic oxidation.
The invention is realized by the following technical scheme:
a method for photo-biomimetic catalytic oxidation of chloride ions and organic matters in sea sand comprises the following steps,
step (1): putting sea sand into a drum mixer, injecting water for mixing, and blowing air into the drum mixer;
step (2): adding metalloporphyrin, a catalyst auxiliary agent and a photosensitizer into the roller in the step (1), continuously stirring and blowing air, and carrying out catalytic oxidation reaction at a certain temperature under a certain illumination condition;
and (3): and (3) after the reaction in the step (2) is finished, carrying out solid-liquid separation on the sea sand and water, washing the sea sand by water, and drying to obtain the finished product sand.
Further, the rotating speed of the drum mixer in the step (1) is 5 r/min-20 r/min.
Further, the flow velocity of the air blown in the step (1) and the step (2) is 5m3/min～20m3/min。
Further, the mass ratio of sea sand to water to solid-liquid in the step (1) is 1: 1.
Further, the amount of the metalloporphyrin used in the step (2) is 0.5 ppm.
Further, the temperature of the catalytic oxidation reaction in the step (2) is 293K-323K.
Further, the time of the catalytic oxidation reaction in the step (2) is 1min to 5 min.
Further, the light source for the catalytic oxidation reaction in the step (2) is ultraviolet light or visible light.
Further, the catalyst promoter in the step (2) is an oxide of iron, and the photosensitizer is an oxygen-containing compound coordinated with porphyrin.
Further, the drying temperature in the step (3) is 293K-333K, and the heat preservation time is 1 h-2 h.
Compared with the prior art, the method has the advantages that the purpose of removing chloride ions is achieved by adding metalloporphyrin to react with chloride ions on the surface of sea sand in water, organic matters can be degraded, a small amount of chlorine and carbon dioxide are generated and are taken out by air flow, and the chlorine and the carbon dioxide are neutralized and solidified by a raw lime absorption tower. The metalloporphyrin photocatalyst can be recycled. The whole process is safe and efficient, and no secondary pollution is worried about.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.
A method for photo-biomimetic catalytic oxidation of chloride ions and organic matters in sea sand comprises the following steps,
step (1): putting sea sand into a drum mixer, injecting water for mixing, and blowing air into the drum mixer;
step (2): adding metalloporphyrin, a catalyst auxiliary agent and a photosensitizer into the roller in the step (1), continuously stirring and blowing air, and carrying out catalytic oxidation reaction at a certain temperature under a certain illumination condition;
and (3): and (3) after the reaction in the step (2) is finished, carrying out solid-liquid separation on the sea sand and water, washing the sea sand by water, and drying to obtain the finished product sand.
The rotating speed of the drum mixer in the step (1) is 5 r/min-20 r/min.
The flow velocity of air blown in the step (1) and the step (2) is 5m3/min～20m3/min。
The mass ratio of sea sand to water to solid in the step (1) is 1: 1.
The consumption of the metalloporphyrin in the step (2) is 0.5 ppm.
The temperature of the catalytic oxidation reaction in the step (2) is 293K-323K.
The time of the catalytic oxidation reaction in the step (2) is 1-5 min.
The light source of the catalytic oxidation reaction in the step (2) is ultraviolet light or visible light.
The catalyst auxiliary agent in the step (2) is iron oxide, and the photosensitizer is an oxygen-containing compound which is coordinated with porphyrin equivalently.
The drying temperature in the step (3) is 293K-333K, and the heat preservation time is 1 h-2 h.
Example 1
Taking primary sea sand taken by seaside for standby:
(1) injecting 1L of water into a 5L roller stirrer, accurately weighing 1kg of primary sea sand, adding into the roller stirrer, starting a stirring device, and adjusting the stirring speed to 15r/min to uniformly mix the water and the sea sand.
(2) Turning on the blower, introducing air, and controlling the air flow rate to be 15m3/min。
(3) After the air flow rate is stabilized, 0.5mg of tetraphenyl carboxyl iron porphyrin (FeTCPP), catalyst auxiliary agent and photosensitizer are added into a roller stirrer, an incandescent lamp is used for simulating visible light, the reaction temperature is maintained at 298K, and the air blowing and stirring are continued for 2 min.
(4) And after the reaction is finished, carrying out solid-liquid separation operation, filtering filtrate, and collecting filter residues.
(5) Washing the filter residue with water, then placing the filter residue in a 313K constant-temperature drying box, preserving heat for 1h, and drying to obtain the finished sand.
Example 2
Taking primary sea sand taken by seaside for standby:
(1) injecting 1L of water into a 5L roller stirrer, accurately weighing 1kg of primary sea sand, adding into the roller stirrer, starting a stirring device, and adjusting the stirring speed to 10r/min to uniformly mix the water and the sea sand.
(2) Turning on the blower, introducing air, and controlling the air flow rate to be 10m3/min。
(3) After the air flow rate is stabilized, 0.5mg of tetra (hydroxyphenyl) ferriporphyrin (FeTHPP), a catalyst auxiliary agent and a photosensitizer are added into the drum mixer, an incandescent lamp is used for simulating visible light, the reaction temperature is maintained at 298K, and the drum air stirring is continued for 1 min.
(4) And after the reaction is finished, carrying out solid-liquid separation operation, filtering filtrate, and collecting filter residues.
(5) Washing the filter residue with water, then placing the filter residue in a 313K constant-temperature drying box, preserving heat for 1h, and drying to obtain the finished sand.
Example 3
Taking primary sea sand taken by seaside for standby:
(1) injecting 1L of water into a 5L roller stirrer, accurately weighing 1kg of primary sea sand, adding into the roller stirrer, starting a stirring device, and adjusting the stirring speed to 20r/min to uniformly mix the water and the sea sand.
(2) Turning on the blower, introducing air, and controlling the air flow rate to be 10m3/min。
(3) After the air flow rate is stabilized, 0.5mg of tetraphenylcarboxylmanganoporphyrin (MnTCPP), a catalyst auxiliary agent and a photosensitizer are added into a roller stirrer, an incandescent lamp is used for simulating visible light, the reaction temperature is maintained at 298K, and the air blowing and stirring are continued for 1 min.
(4) And after the reaction is finished, carrying out solid-liquid separation operation, filtering filtrate, and collecting filter residues.
(5) Washing the filter residue with water, then placing the filter residue in a 313K constant-temperature drying box, preserving heat for 1h, and drying to obtain the finished sand.
Example 4
Taking primary sea sand taken by seaside for standby:
(1) injecting 1L of water into a 5L roller stirrer, accurately weighing 1kg of primary sea sand, adding into the roller stirrer, starting a stirring device, and adjusting the stirring speed to 10r/min to uniformly mix the water and the sea sand.
(2) Turning on the blower, introducing air, and controlling air flow rate to be 20m3/min。
(3) After the air flow rate is stabilized, 0.5mg of tetra (hydroxyphenyl) manganoporphyrin (MnTHPP), a catalyst auxiliary agent and a photosensitizer are added into the drum mixer, an incandescent lamp is used for simulating visible light, the reaction temperature is maintained at 298K, and the drum mixer is continuously aerated and stirred for 2 min.
(4) And after the reaction is finished, carrying out solid-liquid separation operation, filtering filtrate, and collecting filter residues.
(5) Washing the filter residue with water, then placing the filter residue in a 323K constant-temperature drying box, preserving heat for 1 hour, and drying to obtain the finished sand.
And respectively sampling the primary sea sand and the finished product sand sample, and analyzing the change condition of the chloride ions and the organic matters in the primary sea sand and the finished product sand by using a liquid chromatograph to obtain the removal rate of the chloride ions and the organic matters in the sea sand. The results are shown in table 1 below.
Example 5
Taking primary sea sand taken by seaside for standby, and carrying out catalytic oxidation reaction by adopting a common ferric nitrate catalyst:
injecting 1L of water into a 5L roller stirrer, accurately weighing 1kg of primary sea sand, adding into the roller stirrer, starting a stirring device, and adjusting the stirring speed to 15r/min to uniformly mix the water and the sea sand. Turning on the blower, introducing air into water of the drum mixer, and controlling air flow rate to be 15m3And/min. After the air flow rate was stabilized, 0.5mg of ferric nitrate catalyst was added to the drum mixer, an incandescent lamp was used to simulate visible light, the reaction temperature was maintained at 298K, and the drum mixer was continuously aerated and stirred for 2 min. And after the reaction is finished, carrying out solid-liquid separation operation, filtering filtrate, and collecting filter residues. Washing the filter residue with water, then placing the filter residue in a 353K constant-temperature drying box, preserving heat for 1h, and drying to obtain the finished product sand.
Example 6
The method comprises the following steps of taking primary sea sand taken by seaside for standby, and carrying out catalytic oxidation reaction by adopting a common tetraphenylcarboxylporphyrin photocatalyst:
injecting 1L of water into a 5L roller stirrer, accurately weighing 1kg of primary sea sand, adding into the roller stirrer, starting a stirring device, and adjusting the stirring speed to 20r/min to uniformly mix the water and the sea sand. Turning on the blower to the drumIntroducing air into water of the stirrer, and controlling air flow rate to be 10m3And/min. After the air flow rate is stabilized, 0.5mg of tetraphenylcarboxylporphyrin photocatalyst is added into the roller, an incandescent lamp is used for simulating visible light, the reaction temperature is maintained at 298K, and the air blowing and stirring are continued for 2 min. And after the reaction is finished, carrying out solid-liquid separation operation, filtering filtrate, and collecting filter residues. Washing the filter residue with water, then placing the filter residue in a 353K constant-temperature drying box, preserving heat for 1h, and drying to obtain the finished product sand.
And respectively sampling the primary sea sand and the finished product sand sample, and analyzing the change condition of the chloride ions and the organic matters in the primary sea sand and the finished product sand by using a liquid chromatograph to obtain the removal rate of the chloride ions and the organic matters in the sea sand. The results are shown in table 1 below.
Table 1: removal rate of chloride ions and organic matters
| Chloride ion removal rate/%) | Organic matter removal rate/%) | |
| Example 1 | 98 | 99 |
| Example 2 | 97 | 98 |
| Example 3 | 98 | 98 |
| Example 4 | 97 | 99 |
| Example 5 | 25 | 12 |
| Example 6 | 16 | 20 |
As can be seen from the comparison of the table above, the method for the biomimetic catalytic oxidation of the chloride ions and the organic matters in the sea sand provided by the application has a good removing effect on the chloride ions and the organic matters in the sea sand. As shown by the comparison in the table, both the iron porphyrin and the manganese porphyrin which have carboxyl and hydroxyl have good catalytic oxidation effect.
The reaction principle is as follows:
porphyrins are macromolecular heterocyclic compounds formed by four α -carbon atoms containing pyrrole subunits linked by methine bridges (═ CH-) and are widely found in chlorophyll and heme. The four nitrogen atoms of the porphyrin center all contain lone electron pairs which can be coordinated with metal ions to form metalloporphyrin with 18P electron conjugated macrocyclic system structures. The mobility of the electrons in the ring of the porphyrin molecule is very good, so that most metalloporphyrins have good optical properties. Porphyrin as an organic dye has longer excited state life and stronger visible light absorption capacity, and the longer excited state life is more favorable for realizing effective charge separation. The structure of the metalloporphyrin has a large number of lattice defects, and Fe at the defects3+In an unsaturated state, the material with redundant electrons is easy to adsorb or form a complex with the material, so that the material is stable. Due to Fe3+Is the highest valence state of iron, has strong oxidizing property, and can react with chloride ions in water and on the surface of sea sand to generate chlorine gas which is taken away by air, thereby achieving the purpose of removing the chloride ions. Meanwhile, the metalloporphyrin has small volume and large surface areaThe bond state and the electron state on the surface of the particle are different from those in the particle, and the coordination of surface atoms is not equal to that of the surface atoms, so that the active sites on the surface of the particle are increased. The porphyrin generates photo-generated electrons and holes after absorbing light and then is effectively transmitted to Fe in time3+The recombination of photogenerated electron holes is avoided. Under the induction of porphyrin, more photo-generated electrons and holes are rapidly generated, and the photo-generated holes are generated by capturing organic pollutants adsorbed on the surface of the catalyst,-The electrons of OH and the like undergo a series of reactions to generate hydroxyl radicals. Then, the hydroxyl radical attacks the benzene ring and the side chain of the organic matter to break the C-C bond to generate small molecules (such as water, carbon dioxide and the like), thereby achieving the purpose of degrading the organic matter. Therefore, the metalloporphyrin is used as the catalyst, the activity and the selectivity of the metalloporphyrin are higher than those of the common inorganic iron catalyst, the service life is long, the efficiency is high, and the catalytic process is easy to operate.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, but rather as the subject matter of the invention is to be construed in all aspects and equivalents thereof.
Claims (10)
1. A method for photo-biomimetic catalytic oxidation of chloride ions and organic matters in sea sand is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
step (1): putting sea sand into a drum mixer, injecting water for mixing, and blowing air into the drum mixer;
step (2): adding metalloporphyrin, a catalyst auxiliary agent and a photosensitizer into the roller in the step (1), continuously stirring and blowing air, and carrying out catalytic oxidation reaction at a certain temperature under a certain illumination condition;
and (3): and (3) after the reaction in the step (2) is finished, carrying out solid-liquid separation on the sea sand and water, washing the sea sand by water, and drying to obtain the finished sand.
2. The method for the biomimetic catalytic oxidation of chloride ions and organic matters in sea sand according to claim 1, characterized in that: the rotating speed of the drum mixer in the step (1) is 5 r/min-20 r/min.
3. The method for the biomimetic catalytic oxidation of chloride ions and organic matters in sea sand according to claim 1, characterized in that: the flow velocity of air blown in the step (1) and the step (2) is 5m3/min～20m3/min。
4. The method for the biomimetic catalytic oxidation of chloride ions and organic matters in sea sand according to claim 1, characterized in that: the mass ratio of sea sand to water to solid-liquid in the step (1) is 1: 1.
5. The method for the biomimetic catalytic oxidation of chloride ions and organic matters in sea sand according to claim 1, characterized in that: the dosage of the metalloporphyrin in the step (2) is 0.5 ppm.
6. The method for the biomimetic catalytic oxidation of chloride ions and organic matters in sea sand according to claim 1, characterized in that: the temperature of the catalytic oxidation reaction in the step (2) is 293K-323K.
7. The method for the biomimetic catalytic oxidation of chloride ions and organic matters in sea sand according to claim 1, characterized in that: the time of the catalytic oxidation reaction in the step (2) is 1-5 min.
8. The method for the biomimetic catalytic oxidation of chloride ions and organic matters in sea sand according to claim 1, characterized in that: the light source of the catalytic oxidation reaction in the step (2) is ultraviolet light or visible light.
9. The method for the biomimetic catalytic oxidation of chloride ions and organic matters in sea sand according to claim 1, characterized in that: the catalyst auxiliary agent in the step (2) is iron oxide, and the photosensitizer is an oxygen-containing compound which is coordinated with porphyrin equivalently.
10. The method for the biomimetic catalytic oxidation of chloride ions and organic matters in sea sand according to claim 1, characterized in that: the drying temperature in the step (3) is 293K-333K, and the heat preservation time is 1 h-2 h.
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| TW548138B (en) * | 2001-01-03 | 2003-08-21 | Hsi-Tui Hsu | A method for removing harmful ions in sand |
| CN1853784A (en) * | 2005-04-19 | 2006-11-01 | 中国科学院化学研究所 | Method for degrading organic pollutant by light catalyst and its special solid-phase light catalyst |
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| CN110143774A (en) * | 2019-05-29 | 2019-08-20 | 中实泰广(北京)环保科技有限公司 | Sea sand purification system |
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| TW548138B (en) * | 2001-01-03 | 2003-08-21 | Hsi-Tui Hsu | A method for removing harmful ions in sand |
| CN1853784A (en) * | 2005-04-19 | 2006-11-01 | 中国科学院化学研究所 | Method for degrading organic pollutant by light catalyst and its special solid-phase light catalyst |
| CN106396447A (en) * | 2016-11-30 | 2017-02-15 | 国家海洋局第二海洋研究所 | Method for preparing high-performance building sand by desalting sea sand |
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