CN113955741A - Preparation method and application of carbon nanotube macroscopic molding material - Google Patents
Preparation method and application of carbon nanotube macroscopic molding material Download PDFInfo
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- CN113955741A CN113955741A CN202111297305.XA CN202111297305A CN113955741A CN 113955741 A CN113955741 A CN 113955741A CN 202111297305 A CN202111297305 A CN 202111297305A CN 113955741 A CN113955741 A CN 113955741A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 61
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 61
- 239000012778 molding material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 70
- 229920005989 resin Polymers 0.000 claims abstract description 70
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000003756 stirring Methods 0.000 claims abstract description 40
- 239000002253 acid Substances 0.000 claims abstract description 35
- 229910052742 iron Inorganic materials 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 32
- 238000001035 drying Methods 0.000 claims abstract description 19
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 16
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 16
- 230000003197 catalytic effect Effects 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- 230000003647 oxidation Effects 0.000 claims abstract description 13
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000000465 moulding Methods 0.000 claims abstract description 5
- 238000004898 kneading Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 76
- 238000005406 washing Methods 0.000 claims description 48
- 239000003054 catalyst Substances 0.000 claims description 28
- 230000007935 neutral effect Effects 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- -1 iron ion Chemical class 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 239000003513 alkali Substances 0.000 claims description 20
- 238000005342 ion exchange Methods 0.000 claims description 15
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 229920006026 co-polymeric resin Polymers 0.000 claims description 6
- 239000003957 anion exchange resin Substances 0.000 claims description 4
- 230000006835 compression Effects 0.000 claims description 4
- 238000007906 compression Methods 0.000 claims 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 claims description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 3
- 229910001447 ferric ion Inorganic materials 0.000 claims description 3
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000000276 potassium ferrocyanide Substances 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 11
- 239000002245 particle Substances 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 238000005087 graphitization Methods 0.000 abstract description 2
- 238000010000 carbonizing Methods 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 36
- 229910021641 deionized water Inorganic materials 0.000 description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 238000005422 blasting Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
Abstract
The invention relates to a preparation method and application of a carbon nano tube macroscopic molding material, which comprises the following steps: preparing iron ion exchange resin; mixing the prepared iron ion exchange resin, the binder and the acid solution in proportion, stirring and kneading, and drying after molding; calcining under inert atmosphere, and cooling to room temperature to obtain the carbon nanotube macroscopic molding material. The invention has the beneficial effects that: the carbon nanotube structure with high graphitization degree can be generated by carbonizing catalytic resin at high temperature, and the carbon nanotube macroscopic molding material prepared by the method has high catalytic oxidation performance, high pressure resistance and large particle size; the chemical oxidation resistance, the friction resistance and the mechanical strength of the carbon material are improved; has better catalytic application prospect, in particular to the application prospect of ozone catalytic oxidation.
Description
Technical Field
The invention belongs to the technical field of preparation of water treatment catalysts, and particularly relates to a preparation method and application of a carbon nano tube macroscopic molding material.
Background
At present, the problem of wastewater pollution generated in the industries of coal chemical industry, electroplating and the like poses serious threats to the sustainable development of the environment. The ozone oxidation technology is widely applied to the treatment of wastewater at present, but the utilization efficiency of ozone is low, so that the mineralization efficiency is low, and the ozone catalytic oxidation technology can solve the problem to a certain extent.
The carbon nanotube catalyst has a high specific surface area, and is widely used in ozone catalytic oxidation research, but the application of the carbon nanotube catalyst in the actual industry is limited due to poor pressure resistance, small particle size (diameter < 1mm) of the catalyst and the like.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method and application of a carbon nano tube macroscopic molding material.
The preparation method of the carbon nano tube macroscopic molding material comprises the following steps:
step 1, preparing iron ion exchange resin;
step 1.1, carrying out acid washing on resin I: mixing the resin I, acid and water in proportion, stirring, filtering and washing with water to be neutral to obtain a resin II; the resin I is macroporous anion exchange resin;
step 1.2, carrying out alkali washing on the resin II: mixing the resin II, alkali and water in proportion, stirring, filtering and washing with water to be neutral to obtain resin III;
step 1.3, performing iron ion exchange on resin III: mixing the resin III, the iron ion source and water in proportion, stirring, filtering, washing with water to be neutral, and drying to obtain iron ion exchange resin;
step 2, mixing the iron ion exchange resin prepared in the step 1, a binder and an acid solution in proportion, stirring and kneading, and drying after molding; calcining under inert atmosphere, and cooling to room temperature to obtain the carbon nanotube macroscopic molding material.
Preferably, the acid used for acid washing in step 1.1 includes hydrochloric acid, nitric acid, sulfuric acid and hydrofluoric acid; the macroporous anion exchange resin comprises styrene-divinylbenzene copolymer resin, acrylic acid copolymer resin and styrene-divinylbenzene copolymer resin containing quaternary ammonium groups.
Preferably, in the step 1.1, the resin I, the acid and the water are mixed according to the proportion of (100-1000 g) to (20-200 mL) to (150-2000 mL), and stirred for 6-24 h.
Preferably, in the step 1.1, the resin I, the acid and the water are mixed according to the proportion of (100-1000 g) to (20-150 mL) to (150-500 mL);
preferably, in the step 1.1, the resin I, the acid and the water are mixed according to the proportion of (100-500 g) to (20-100 mL) to (150-300 mL);
preferably, in the step 1.1, the resin I, the acid and the water are mixed according to the proportion of (100-200 g) to (20-50 mL) to (150-300 mL);
preferably, the stirring time of the mixture of resin i, acid and water in step 1.1 is any one of 6h, 8h, 12h, 15h, 18h, 24h or a range between any two values.
Preferably, the alkali used for the alkali washing in step 1.2 comprises sodium hydroxide and potassium hydroxide; mixing the resin II, alkali and water according to the proportion of (100-1000 g) to (8-100 g) to (150-2000 mL), and stirring for 6-24 h.
Preferably, in the step 1.2, the resin II, the alkali and the water are mixed according to the proportion of (100-800 g) to (8-80 g) to (150-1000 mL).
Preferably, in the step 1.2, the resin II, the alkali and the water are mixed according to the proportion of (100-500 g) to (8-50 g) to (150-800 mL).
Preferably, in the step 1.2, the resin II, the alkali and the water are mixed according to the proportion of (100-200 g): (8-20 g): 150-300 mL).
Preferably, the stirring time of the mixture of resin ii, base and water in step 1.2 is any one value or a range between any two values of 6h, 8h, 12h, 15h, 18h and 24 h.
Preferably, the ferric ion source in step 1.3 comprises ferric chloride, ferrous chloride, ferric nitrate, ferrous sulfate, potassium ferricyanide and potassium ferrocyanide; and mixing the resin III, the iron ion source and water according to the proportion of (100-1000 g) - (15-200 g) - (300-5000 mL), stirring for 1-24 h, washing with water to be neutral, and drying at 80-120 ℃ to obtain the iron ion exchange resin.
Preferably, the resin III, the iron ion source and water are mixed in a ratio of (100-700 g): (15-80 g): 300-1000 mL.
Preferably, the resin III, the iron ion source and water are mixed in a ratio of (100-500 g): (15-50 g): 300-500 mL.
Preferably, the resin III, the iron ion source and water are mixed in a ratio of (100-200 g): (15-30 g): 300-400 mL.
Preferably, the stirring time of the mixture of resin iii, the source of ferric ions and water in step 1.3 is any one of 1h, 6h, 8h, 12h, 15h, 18h, 24h or a range of values between any two of these values.
Preferably, the binder in step 2 comprises pseudo-boehmite, alumina sol and silica sol, and the acid solution comprises nitric acid, hydrochloric acid, sulfuric acid and hydrofluoric acid; the concentration of the acid solution is 1-10% by mass percent.
Preferably, the concentration of the acid solution in step 2 is any one value or a range between any two values among 1%, 3%, 5%, 8%, and 10%.
Preferably, in the step 2, the iron ion exchange resin, the binder and the acid solution are mixed according to the proportion of 100g (100-300 g) to 80-180 mL, stirred for 0.1-1.5 h, and dried for 12-24 h at 80-120 ℃ after being formed; calcining the carbon nano tube at 500-1000 ℃ for 1-6 h in an inert atmosphere, and cooling to room temperature to obtain the carbon nano tube macroscopic molding material.
Preferably, in the step 2, the iron ion exchange resin, the binder and the acid solution are mixed according to the proportion of 100g (100-200 g) to 80-150 mL.
Preferably, in the step 2, the iron ion exchange resin, the binder and the acid solution are mixed according to the proportion of 100g (100-150 g) to 80-100 mL.
Preferably, the inert atmosphere in step 2 is a nitrogen atmosphere.
Preferably, in the step 2, after the molded iron ion exchange resin, the binder and the acid solution mixture are calcined, the calcination time in the inert atmosphere is selected from any one value or a range between any two values of 1h, 2h, 3h, 4h, 5h and 6 h; the calcination temperature is selected from any one value or a range between any two values of 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃.
Preferably, the carbon nanotube macroscopic molding material prepared in the step 2 is a cylinder with the diameter of 1-5 mm and the length of 5-50 mm, or a sphere with the diameter of 1-5 mm; the compression resistance of the carbon nanotube macroscopic molding material is 50-400N/cm; the microscopic diameter of the carbon nanotube macroscopic molding material prepared in the step 2 is 5-100 nm.
Preferably, the carbon nanotube macroscopic molding material prepared in the step 2 is a cylinder with the diameter of 2-5 mm and the length of 8-40 mm.
Preferably, when the carbon nanotube macroscopic molding material is a cylinder, the diameter of the cylinder is any one value or a range of any two values of 1mm, 3mm and 5mm, and the length of the cylinder is selected from any one value or a range of any two values of 5mm, 8mm, 10mm, 15mm, 20mm, 30mm, 40mm and 50 mm.
Preferably, when the carbon nanotube macroscopic molding material is a sphere, the diameter is any one value or a range between any two values of 1mm, 3mm and 5 mm.
Preferably, the microscopic diameter of the carbon nanotube macroscopic molding material is selected from any one value or a range between any two values of 5nm, 10nm, 20nm, 40nm, 50nm, 70nm, 80nm, 90nm and 100 nm.
Preferably, the prepared carbon nanotube macroscopic molding material is used as a catalyst and/or a catalyst carrier in water treatment catalytic oxidation.
The invention has the beneficial effects that:
in order to better apply the ozone catalytic oxidation in the field of water treatment, the invention provides a preparation method of a carbon nano tube macroscopic molding material, resin is subjected to acid washing, alkali washing and iron ion exchange, and the resin can be catalyzed to carbonize at high temperature to generate a carbon nano tube structure with high graphitization degree, and the prepared carbon nano tube macroscopic molding material has high catalytic oxidation performance, good compression resistance and large particle size; the chemical oxidation resistance, the friction resistance and the mechanical strength of the carbon material are improved; has better catalytic application prospect, in particular to the application prospect of ozone catalytic oxidation.
According to the preparation method of the carbon nanotube macroscopic molding material, the iron ion exchange resin, the binder and the acid solution are molded and then calcined to prepare the carbon nanotube macroscopic molding material, the process is simple, the particle size of the target carbon nanotube catalyst is easy to control, and the mechanical strength of the obtained carbon nanotube macroscopic molding material is ensured.
The invention prepares the carbon nano tube catalyst by molding the resin with the pseudo-boehmite, improves the compression resistance and the particle size, solves the problem that most of the existing carbon nano tube catalysts are powder and are difficult to be practically applied, and provides a production method which has low cost and can realize industrialization for preparing the catalyst with large particle size and high mechanical property.
Drawings
FIG. 1 is an optical photograph of a sample of C1# prepared in example 1 of the present invention;
FIG. 2 is a microscopic structure diagram of a sample C1# prepared in example 1 according to the present invention under a transmission electron microscope;
FIG. 3 is an optical photograph of a sample C2# prepared in example 2 of the present invention;
FIG. 4 is a schematic diagram of the method for testing the mechanical properties of the carbon nanotube macroscopic modeling material according to the present invention;
FIG. 5 is a graph showing the results of mechanical property tests on samples C1# prepared in example 1 of the present invention;
FIG. 6 is a schematic diagram of an ozone catalytic oxidation wastewater performance testing device.
Detailed Description
The present invention will be further described with reference to the following examples. The following examples are set forth merely to aid in the understanding of the invention. It should be noted that, for a person skilled in the art, several modifications can be made to the invention without departing from the principle of the invention, and these modifications and modifications also fall within the protection scope of the claims of the present invention.
In the invention, the room temperature is 15-35 ℃, the natural drying temperature is 15-35 ℃, and the percentages are mass percentages.
Example 1: preparation and performance testing of cylindrical carbon nanotube catalyst
Acid washing in step (1): uniformly mixing 100g of styrene-divinylbenzene resin, 20mL of concentrated hydrochloric acid (the mass fraction is about 37%) and 180mL of deionized water in a beaker, stirring for 12 hours, and then washing with deionized water to be neutral;
alkali washing in step (2): putting 100g of the resin obtained in the step (1) into a beaker with alkaline cleaning, mixing with 8g of sodium hydroxide and 192mL of deionized water, stirring for 12h, and then washing with deionized water to be neutral;
step (3), iron ion exchange: putting 100g of the resin obtained in the step (2) into an ion exchange beaker, mixing with 15g of potassium ferricyanide and 300mL of deionized water, stirring for 6h, washing with deionized water to be neutral, and drying the resin exchanged with the potassium ferricyanide at the temperature of 80 ℃;
and (4) forming: 100g of the exchanged resin obtained in the step (3) was mixed with 100g of pseudo-boehmite, and 80mL of 3% nitric acid was added thereto and kneaded in a mixer. Stirring for 0.5h, taking out, putting into a strip extruding machine, extruding into strips, and cutting to obtain cylinders with the diameter of 3mm and the length of 10 mm;
and (5) drying: naturally drying the formed precursor obtained in the step (4) in the air for 24 hours, and then drying the formed precursor in a drying oven for 12 hours at the temperature of 80 ℃;
and (6) calcining: and (5) putting the cylindrical particles obtained in the step (5) into a tubular furnace, and heating to 600 ℃ for calcining for 5 hours under the protection of nitrogen. And after the calcination is finished, naturally cooling to room temperature.
The obtained carbon nanotube catalyst was recorded as sample C1# and the optical photograph thereof is shown in FIG. 1, which is a cylinder with a diameter of 3mm and a length of 10 mm; the microstructure under a transmission electron microscope is shown in FIG. 2, and the result shows that the microscopic diameter of the carbon nanotube in the sample C1# is about 70 nm.
Mechanical property test of sample C1 #:
the test method of the compressive strength is carried out according to the method for measuring the crushing resistance of the HG/T2782-2011 fertilizer catalyst particles. After taking a single sample from the samples and measuring the length of the single sample on a vernier caliper, placing the side of the single sample on a sample platform of a strength tester to be stable to be not rolled, starting a working key of the particle strength tester, and gradually stressing the sample until the sample is broken. The schematic diagram of the test method is shown in fig. 4.
Calculation of the results:
the radial crush force F, expressed in newtons per centimeter (N/cm) of resin, is calculated as follows:
in the above formula:
f' — the value in newtons (N) displayed by the tester when the sample was broken;
l is a value of the length of the sample in centimeters (cm).
As shown in FIG. 5, the radial compressive strength was 95N/cm.
Catalytic performance testing of sample C1 #:
adopting a self-made vertical tubular flow reactor (as shown in figure 6), introducing ozone and coal chemical wastewater raw water with COD (chemical oxygen demand) of 100mg/L into the bottom, discharging water from the top, sampling every 30 minutes, and working condition parameters: the water flow is 0.14L/h, the gas flow is 0.5L/h, the retention time is 16.8min, the ozone concentration is 60mg/L, and the gas-liquid ratio is 214 mg/L. And detecting the taken water sample by using a total organic carbon analyzer.
The result shows that the Total Organic Carbon (TOC) removal rate in the wastewater reaches 63 percent after the ozone catalytic oxidation reaction is carried out for 1.5 hours.
Example 2: preparation of spherical carbon nanotube catalyst
Steps (1) to (3) are the same as in example 1;
and (4) forming: 100g of the exchanged resin obtained in the step (3) was mixed with 100g of pseudo-boehmite, and 80mL of 3% nitric acid was added thereto and kneaded in a mixer. Stirring for 0.5h, taking out, putting into a strip extruding machine, extruding into strips, cutting, and shaping into spheres with the diameter of 3mm by using a shot blasting machine;
steps (5) to (6) are the same as in example 1.
The obtained carbon nanotube catalyst was designated as sample C2# and its optical photograph is shown in FIG. 3, which is a spherical body with a diameter of 3 mm.
Example 3: preparation of cylindrical carbon nanotube catalyst
Acid washing in step (1): uniformly mixing 100g of styrene-divinylbenzene resin, 80mL of concentrated hydrochloric acid (the mass fraction is about 37%) and 180mL of deionized water in a beaker, stirring for 12 hours, and then washing with deionized water to be neutral;
alkali washing in step (2): putting 100g of the resin obtained in the step (1) into a beaker with alkaline cleaning, mixing with 32g of sodium hydroxide and 192mL of deionized water, stirring for 12 hours, and then washing with deionized water to be neutral;
step (3), iron ion exchange: putting 100g of the resin obtained in the step (2) into an ion exchange beaker, mixing with 60g of potassium ferricyanide and 300mL of deionized water, stirring for 6h, washing with deionized water to be neutral, and drying the resin exchanged with the potassium ferricyanide at the temperature of 80 ℃;
steps (4) to (6) are the same as in example 1.
Example 4: preparation of cylindrical carbon nanotube catalyst
Acid washing in step (1): uniformly mixing 100g of styrene-divinylbenzene resin, 100mL of concentrated hydrochloric acid (the mass fraction is about 37%) and 180mL of deionized water in a beaker, stirring for 12 hours, and then washing with deionized water to be neutral;
alkali washing in step (2): putting 100g of the resin obtained in the step (1) into a beaker with alkaline washing, mixing with 40g of sodium hydroxide and 192mL of deionized water, stirring for 12 hours, and then washing with deionized water to be neutral;
step (3), iron ion exchange: putting 100g of the resin obtained in the step (2) into an ion exchange beaker, mixing with 75g of potassium ferricyanide and 300mL of deionized water, stirring for 6h, washing with deionized water to be neutral, and drying the resin exchanged with the potassium ferricyanide at the temperature of 80 ℃;
steps (4) to (6) are the same as in example 1.
Example 5: preparation of spherical carbon nanotube catalyst
Steps (1) to (3) were the same as in example 3
And (4) forming: 100g of the exchanged resin obtained in the step (3) was mixed with 200g of pseudo-boehmite, and 120mL of 3% nitric acid was added thereto and kneaded in a mixer. Stirring for 1h, taking out, putting into a strip extruding machine, extruding into strips, cutting, and shaping into spheres with the diameter of 3mm by using a shot blasting machine;
steps (5) to (6) are the same as in example 1.
Example 6: preparation of spherical carbon nanotube catalyst
The steps (1) to (3) are the same as in example 4;
and (4) forming: 100g of the exchanged resin obtained in the step (3) was mixed with 300g of pseudo-boehmite, and 180mL of 3% nitric acid was added thereto and kneaded in a mixer. Stirring for 1.5h, taking out, putting into a strip extruding machine, extruding into strips, cutting, and shaping into spheres with the diameter of 3mm by using a shot blasting machine;
steps (5) to (6) are the same as in example 1.
Example 7: preparation of cylindrical carbon nanotube catalyst
Steps (1) to (5) are the same as in example 1;
and (6) calcining: and (5) putting the cylindrical particles obtained in the step (5) into a tube furnace, and heating to 500 ℃ under the protection of nitrogen for calcining for 6 hours. And after the calcination is finished, naturally cooling to room temperature.
Example 8: preparation of cylindrical carbon nanotube catalyst
Steps (1) to (5) are the same as in example 1;
and (6) calcining: and (5) putting the cylindrical particles obtained in the step (5) into a tubular furnace, and heating to 1000 ℃ for calcining for 1h under the protection of nitrogen. And after the calcination is finished, naturally cooling to room temperature.
Example 9: preparation of cylindrical carbon nanotube catalyst
Acid washing in step (1): uniformly mixing 100g of acrylic copolymer resin, 30mL of concentrated hydrochloric acid (mass fraction is about 37%) and 170mL of deionized water in a beaker, stirring for 12 hours, and washing with deionized water to be neutral;
alkali washing in step (2): putting 100g of the resin obtained in the step (1) into a beaker with alkaline cleaning, mixing with 15g of sodium hydroxide and 300mL of deionized water, stirring for 12h, and then washing with deionized water to be neutral;
step (3), iron ion exchange: putting 100g of the resin obtained in the step (2) into an ion exchange beaker, mixing with 15g of potassium ferricyanide and 300mL of deionized water, stirring for 6h, washing with deionized water to be neutral, and drying the resin exchanged with the potassium ferricyanide at the temperature of 80 ℃;
steps (4) to (6) are the same as in example 1.
Example 10: preparation of cylindrical carbon nanotube catalyst
Acid washing in step (1): uniformly mixing 100g of styrene-divinylbenzene copolymer resin containing quaternary ammonium groups, 50mL of concentrated hydrochloric acid (the mass fraction is about 37%) and 150mL of deionized water in a beaker, stirring for 12 hours, and then washing with deionized water to be neutral;
alkali washing in step (2): putting 100g of the resin obtained in the step (1) into a beaker with alkaline cleaning, mixing with 20g of sodium hydroxide and 400mL of deionized water, stirring for 12h, and then washing with deionized water to be neutral;
step (3), iron ion exchange: putting 100g of the resin obtained in the step (2) into an ion exchange beaker, mixing with 20g of potassium ferricyanide and 300mL of deionized water, stirring for 6h, washing with deionized water to be neutral, and drying the resin exchanged with the potassium ferricyanide at the temperature of 80 ℃;
steps (4) to (6) are the same as in example 1.
Example 11: preparation of spherical carbon nanotube catalyst
Acid washing in step (1): uniformly mixing 100g of styrene-divinylbenzene copolymer resin containing quaternary ammonium groups, 20mL of concentrated hydrochloric acid (the mass fraction is about 37%) and 180mL of deionized water in a beaker, stirring for 12 hours, and washing with deionized water to be neutral;
alkali washing in step (2): putting 100g of the resin obtained in the step (1) into a beaker with alkaline cleaning, mixing with 8g of sodium hydroxide and 192mL of deionized water, stirring for 12h, and then washing with deionized water to be neutral;
step (3), iron ion exchange: putting 100g of the resin obtained in the step (2) into an ion exchange beaker, mixing with 15g of potassium ferricyanide and 300mL of deionized water, stirring for 6h, washing with deionized water to be neutral, and drying the resin exchanged with the potassium ferricyanide at the temperature of 80 ℃;
and (4) forming: 100g of the exchanged resin obtained in the step (3) was mixed with 200g of pseudo-boehmite, and 120mL of 3% nitric acid was added thereto and kneaded in a mixer. Stirring for 1h, taking out, putting into a strip extruding machine, extruding into strips, cutting, and shaping into spheres with the diameter of 3mm by using a shot blasting machine;
steps (5) to (6) are the same as in example 1.
Claims (10)
1. A method for preparing a carbon nano tube macroscopic molding material is characterized by comprising the following steps:
step 1, preparing iron ion exchange resin;
step 1.1, carrying out acid washing on resin I: mixing the resin I, acid and water in proportion, stirring, filtering and washing with water to be neutral to obtain a resin II; the resin I is macroporous anion exchange resin;
step 1.2, carrying out alkali washing on the resin II: mixing the resin II, alkali and water in proportion, stirring, filtering and washing with water to be neutral to obtain resin III;
step 1.3, performing iron ion exchange on resin III: mixing the resin III, the iron ion source and water in proportion, stirring, filtering, washing with water to be neutral, and drying to obtain iron ion exchange resin;
step 2, mixing the iron ion exchange resin prepared in the step 1, a binder and an acid solution in proportion, stirring and kneading, and drying after molding; calcining under inert atmosphere, and cooling to room temperature to obtain the carbon nanotube macroscopic molding material.
2. The method for preparing a carbon nanotube macroscopic molding material according to claim 1, wherein: the acid adopted in the acid cleaning in the step 1.1 comprises hydrochloric acid, nitric acid, sulfuric acid and hydrofluoric acid; the macroporous anion exchange resin comprises styrene-divinylbenzene copolymer resin, acrylic acid copolymer resin and styrene-divinylbenzene copolymer resin containing quaternary ammonium groups.
3. The method for preparing a carbon nanotube macroscopic molding material according to claim 1, wherein: in the step 1.1, the resin I, the acid and the water are mixed according to the proportion of (100-1000 g) to (20-200 mL) to (150-2000 mL), and stirred for 6-24 h.
4. The method for preparing a carbon nanotube macroscopic molding material according to claim 1, wherein: the alkali adopted in the alkali washing in the step 1.2 comprises sodium hydroxide and potassium hydroxide; mixing the resin II, alkali and water according to the proportion of (100-1000 g) to (8-100 g) to (150-2000 mL), and stirring for 6-24 h.
5. The method for preparing a carbon nanotube macroscopic molding material according to claim 1, wherein: in the step 1.3, the ferric ion source comprises ferric chloride, ferrous chloride, ferric nitrate, ferrous sulfate, potassium ferricyanide and potassium ferrocyanide; and mixing the resin III, the iron ion source and water according to the proportion of (100-1000 g) - (15-200 g) - (300-5000 mL), stirring for 1-24 h, filtering, washing with water to be neutral, and drying at 80-120 ℃ to obtain the iron ion exchange resin.
6. The method for preparing a carbon nanotube macroscopic molding material according to claim 1, wherein: in the step 2, the binder comprises pseudo-boehmite, aluminum sol and silica sol, and the acid solution comprises nitric acid, hydrochloric acid, sulfuric acid and hydrofluoric acid; the concentration of the acid solution is 1-10% by mass percent.
7. The method for preparing a carbon nanotube macroscopic molding material according to claim 1, wherein: mixing the iron ion exchange resin, the binder and the acid solution according to the proportion of 100g (100-300 g) to 80-180 mL, stirring and kneading for 0.1-1.5 h, and drying at 80-120 ℃ for 12-24 h after molding; calcining the carbon nano tube at 500-1000 ℃ for 1-6 h in an inert atmosphere, and cooling to room temperature to obtain the carbon nano tube macroscopic molding material.
8. The method for preparing a carbon nanotube macroscopic molding material according to claim 1, wherein: the inert atmosphere in step 2 is a nitrogen atmosphere.
9. The method for preparing a carbon nanotube macroscopic molding material according to claim 1, wherein: the macroscopic molding material of the carbon nano tube prepared in the step 2 is a cylinder with the diameter of 1-5 mm and the length of 5-50 mm, or a sphere with the diameter of 1-5 mm; the compression resistance of the carbon nanotube macroscopic molding material is 50-400N/cm; the microscopic diameter of the carbon nanotube macroscopic molding material prepared in the step 2 is 5-100 nm.
10. Use of a method for the preparation of a carbon nanotube macroscopic molding material according to any one of claims 1 to 9 in catalysts and/or catalyst supports, characterized in that: the prepared carbon nano tube macroscopic molding material is used as a catalyst and/or a catalyst carrier in water treatment catalytic oxidation.
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