CN113680349A - Preparation method of coal-based active coke-based ozone catalyst for treating coking wastewater - Google Patents
Preparation method of coal-based active coke-based ozone catalyst for treating coking wastewater Download PDFInfo
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- CN113680349A CN113680349A CN202111140514.3A CN202111140514A CN113680349A CN 113680349 A CN113680349 A CN 113680349A CN 202111140514 A CN202111140514 A CN 202111140514A CN 113680349 A CN113680349 A CN 113680349A
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- coke
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- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000000571 coke Substances 0.000 title claims abstract description 38
- 239000003245 coal Substances 0.000 title claims abstract description 23
- 238000004939 coking Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002351 wastewater Substances 0.000 title claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000003763 carbonization Methods 0.000 claims abstract description 23
- 238000001994 activation Methods 0.000 claims abstract description 21
- 230000004913 activation Effects 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000004898 kneading Methods 0.000 claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 239000011230 binding agent Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000000465 moulding Methods 0.000 claims abstract description 5
- 239000012634 fragment Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 8
- 239000005751 Copper oxide Substances 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 8
- 229910000431 copper oxide Inorganic materials 0.000 claims description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- 239000012778 molding material Substances 0.000 claims description 8
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000002802 bituminous coal Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 4
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003830 anthracite Substances 0.000 claims description 2
- 239000011300 coal pitch Substances 0.000 claims description 2
- 239000011280 coal tar Substances 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 238000005507 spraying Methods 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 15
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000004065 wastewater treatment Methods 0.000 abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 5
- 239000011812 mixed powder Substances 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000010426 asphalt Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- -1 polycyclic nitrogen-containing aromatic hydrocarbons Chemical class 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
-
- 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
- C02F2101/30—Organic compounds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a coal-based active coke-based ozone catalyst for treating coking wastewater, belonging to the field of catalysts for coking wastewater treatment. The preparation method comprises the following steps: grinding raw coal, semi-coke and active components into fine powder, mixing, adding water, a binder and an auxiliary agent into the mixed powder, stirring and kneading, molding the kneaded material, drying or drying the molded body until the water content is 5-15%, carrying out carbonization and activation, and removing powder and fragments by using an upper sieve of the carbonization and activation catalyst to obtain a catalyst finished product. The invention takes coal-made active coke as a main carrier, and has the advantages of the traditional carbon-based catalyst and the traditional alumina or silicon-aluminum-based catalyst: the raw materials are easy to obtain, the preparation is simple, the cost is low, and meanwhile, the effect is excellent when the coking wastewater COD is treated.
Description
Technical Field
The invention relates to the field of catalysts for coking wastewater treatment, in particular to a preparation method of a coal-made active coke-based ozone catalyst and the coal-made active coke-based ozone catalyst prepared by the method.
Background
Coking wastewater is wastewater generated in the processes of coking, coal gas high-temperature dry distillation, purification and byproduct recovery of steel enterprises, and the wastewater contains complex inorganic and organic pollutants, such as phenols, cyanides, thiocyanides, ammonia, polycyclic aromatic hydrocarbons, polycyclic nitrogen-containing aromatic hydrocarbons, sulfur-containing heterocyclic compounds and the like, most of which are refractory, toxic and carcinogenic substances, and the traditional biochemical treatment method has poor effect of removing the substances. The ozone catalytic oxidation technology can be carried out at normal temperature and normal pressure, does not need any heat, light or high-pressure auxiliary system, is an environment-friendly advanced oxidation technology, and is particularly suitable for removing organic pollutants difficult to degrade in water.
Ozone has strong oxidation effect, the oxidation-reduction potential of the ozone is 2.07eV, although pure ozone oxidation can remove organic matters to a certain extent, the pollutant is not thoroughly treated under the condition of low utilization rate of the single ozone. The ozone catalytic oxidation technology is a novel advanced oxidation technology developed on the basis of the traditional ozone oxidation, and a catalyst is added into an ozone system, so that on one hand, the catalyst can also adsorb pollutants on the surface of the catalyst, and the capability of directly oxidizing organic matters by ozone is improved; on the other hand, the method can obviously improve the generation of hydroxyl radicals with stronger oxidizing capability in an ozone system and degrade pollutants. Ozone catalysts are generally divided into homogeneous catalysts and heterogeneous catalysts, the homogeneous catalysts are generally transition metal ions, the catalysts run away with water after treatment, and the running-away metal ions have potential environmental safety risks; the heterogeneous ozone catalyst mainly utilizes the catalytic action of solid metal, metal oxide or metal oxide loaded on a carrier, has the advantages of simple preparation, easy recovery treatment, long service life and the like, and has wide application in engineering.
The common heterogeneous ozone catalyst is generally prepared by taking active carbon or alumina or a silicon-aluminum composite material as a carrier, loading metal salts such as iron, manganese and the like on the carrier by adopting an impregnation method, and then drying, roasting and the like processes on the carrier.
When the catalyst is prepared by taking the active carbon as a carrier, the organic pollutants can be removed by utilizing the adsorption effect of the active carbon, but the catalyst is easy to run off and short in service life, and the columnar product can increase the head loss of backwashing; the catalyst prepared by the alumina or silicon-aluminum composite material has high strength and long service life, but the raw materials are expensive, the temperature required in the roasting process is higher, the energy consumption is high, the density of the catalyst is higher, the requirement on the strength of a tank device in industrial application is higher, and the cost in engineering application is higher.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a coal-made active coke-based ozone catalyst, the coal-made active coke-based ozone catalyst prepared by the method and the application of the catalyst in treating coking wastewater. The coal-made active coke-based ozone catalyst has the advantages that the coal-made active coke is used as a carrier, and a certain proportion of active components and auxiliaries are added by a blending type preparation process aiming at the characteristics of refractory substances such as polycyclic aromatic hydrocarbon, cyanide, nitrogen-containing heterocyclic compounds and the like contained in coking wastewater, so that the defects of short service life of the active carbon catalyst and high cost of the alumina or silicon-aluminum-based catalyst are overcome, and the coal-made active coke-based ozone catalyst which has the advantages of large specific surface area, high compressive strength, long service life, good binding property of the active components and the carrier, high stability, low cost and higher efficiency of exciting to generate hydroxyl radicals is obtained.
The purpose of the invention is realized by the following technical scheme:
a preparation method of an active coke-based ozone catalyst for coal production comprises the following steps:
(1) grinding: raw coal, semi coke and active components are mixed according to the mass ratio of (30-75): (20-60): (5-10) weighing, grinding into fine powder and mixing. The active component is a mixture of any two or more than two of manganese oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide and cerium oxide. This step is preferably carried out in a ball mill.
(2) Stirring and kneading: and (2) adding water, a binder and an auxiliary agent into the ground and mixed powder in the step (1) for stirring and kneading, wherein the adding amount of the water accounts for 10-25% of the mass of the powder, the adding amount of the binder accounts for 10-30% of the mass of the powder, and the adding amount of the auxiliary agent accounts for 0.1-5% of the mass of the powder. The assistant is an alkaline solution containing one or more metal ions, the metal ions comprise potassium, sodium, magnesium and other metal ions, and the total metal ion solubility in the alkaline solution is preferably 100-1000 mg/L. The powder quality in the step refers to the quality of mixed powder of raw coal, semi coke and active components. This step is preferably carried out in a kneader.
(3) Molding: and (3) molding the kneaded material kneaded in the step (2). Preferably in a disk pelletizer and finally formed into round pellet shapes. The molded article obtained was air-dried or dried to a water content of 5 to 15%, and then subjected to the next step.
(4) Carbonization and activation: and (4) carbonizing and activating the molding material in the step (3). Firstly, heating a carbonization activation device to a preset temperature, enabling the molding material to have a carbonization reaction, maintaining for a period of time, and then heating to activate the molding material. The carbonization is performed in a non-oxidizing atmosphere such as nitrogen. The activation is carried out under a non-oxidizing atmosphere consisting of nitrogen gas and water vapor. This step is preferably accomplished in a carbonization activation furnace.
(5) Cooling and screening: and (4) naturally cooling the carbonized and activated catalyst in the step (4), and then sieving to remove powder and fragments to obtain a catalyst finished product. If the step (4) is completed in the carbonization and activation furnace, the carbonized and activated catalyst is taken out of the furnace and then naturally cooled; the tapping temperature is below 100 ℃, preferably below 70 ℃.
In the step (1), the raw coal can be bituminous coal or anthracite; the particle size of the fine powder is preferably 200 meshes or more.
In the step (1), the ball mill can stir and mix the raw materials by mechanically milling.
In the step (1), when the active components are any two of manganese oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide and cerium oxide, the mass ratio of the two is preferably (1-5): (1-5).
In the step (2), the binder is preferably one or more of coal tar, pitch and glycerol.
In the step (2), the assistant is preferably a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution or a mixed aqueous solution of sodium hydroxide and potassium hydroxide.
In the step (2), the kneading time is preferably 10 to 30 min.
In the step (3), the diameter of the granules is preferably controlled to be 4-6mm, and the standard is 5 mm; when the water content of the ball material is 5-15%, the compressive strength is above 10 MPa.
In the step (3), the drying temperature is preferably 50 to 90 ℃.
In the step (4), the carbonization temperature rise rate is controlled to be 5-20 ℃/min, the carbonization reaction temperature is 500-800 ℃, and the carbonization reaction time is 0.5-3 h.
In the step (4), the activation temperature rate is controlled to be 5-20 ℃/min, the activation reaction temperature is 500-900 ℃, and the activation reaction time is 10-120 min.
In the step (4), the amount of water vapor injected is preferably 5.0 to 20mL/min/500g of molding material in a non-oxidizing atmosphere consisting of nitrogen and water vapor.
An active coke-based ozone catalyst for coal production, which is obtained by the preparation method.
The coal-made active coke-based ozone catalyst is applied to treatment of coking wastewater.
Compared with the prior art, the invention has the following advantages and beneficial effects: the invention takes coal-made active coke as a main carrier, and has the advantages of the traditional carbon-based catalyst and the traditional alumina or silicon-aluminum-based catalyst: the raw materials are easy to obtain, the preparation is simple, the cost is low, and meanwhile, the effect is excellent when the coking wastewater COD is treated.
Detailed Description
The following examples are intended to further illustrate the invention but should not be construed as limiting it. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.
Example 1:
the preparation of the coal-made active coke-based ozone catalyst for treating the coking wastewater comprises the following steps:
(1) weighing and mixing bituminous coal, semi-coke and active components according to the mass ratio of 55:40:5, pouring the mixture into a ball mill, grinding the mixture into fine powder with the particle size of more than 200 meshes, and mixing the fine powder, wherein the total mass is 5 kg. The active component is a mixture consisting of copper oxide and cerium oxide, and the mass ratio of the copper oxide to the cerium oxide is 1: 1.
(2) Pouring the powder ground and mixed in the step (1) into a kneader, adding 1kg of water, 0.75kg of asphalt and 0.05kg of sodium hydroxide solution with the sodium ion concentration of 100mg/L, and kneading for 15 min.
(3) And (3) feeding the kneaded material kneaded in the step (2) into a disc granulator for granulation, controlling the diameter of the spherical particles to be 4-6mm, and airing the spherical particles until the water content is 10% and the compressive strength is 12MPa after the spherical particles are formed.
(4) And (4) carbonizing and activating the ball material treated in the step (3). And (3) feeding the ball material into a carbonization and activation furnace, setting the temperature at 600 ℃, the heating rate at 5 ℃/min and the carbonization time at 1h, and carbonizing in a nitrogen atmosphere. After carbonization, the temperature in the furnace is set to 700 ℃, the heating rate is 10 ℃/min, the activation time is 20min, activation is carried out in the atmosphere consisting of nitrogen and water vapor, and the injection amount of the water vapor is 5.0mL/min/500g of the formed ball material.
(5) And (4) cooling the ball material treated in the step (4) to below 70 ℃, discharging, naturally cooling, sieving to remove powder and fragments, and obtaining a finished product of the coal-based active coke-based ozone catalyst, wherein the number of the finished product is the catalyst A.
Example 2:
(1) weighing and mixing bituminous coal, semi-coke and active components according to the mass ratio of 55:40:0, pouring the mixture into a ball mill, grinding the mixture into fine powder with the particle size of more than 200 meshes, and mixing the fine powder, wherein the total mass is 5 kg.
(2) Pouring the powder ground and mixed in the step (1) into a kneader, adding 1kg of water, 0.75kg of asphalt and 0kg of sodium hydroxide solution with the concentration of 100mg/L, and kneading for 15 min.
(3) The remaining steps were carried out according to the steps (3), (4) and (5) in example 1.
Finally, the coal-made active coke ozone catalyst without active components and auxiliaries is prepared, and the number of the catalyst is the catalyst B.
Example 3
(1) Weighing and mixing bituminous coal, semi-coke and active components according to the mass ratio of 55:40:5, pouring the mixture into a ball mill, grinding the mixture into fine powder with the particle size of more than 200 meshes, and mixing the fine powder, wherein the total mass is 5 kg. The active component is a mixture consisting of copper oxide and cerium oxide, and the mass ratio of the copper oxide to the cerium oxide is 1: 1.
(2) Pouring the powder ground and mixed in the step (1) into a kneader, adding 1kg of water, 0.75kg of asphalt and 0kg of sodium hydroxide solution with the concentration of 100mg/L, and kneading for 15 min.
(3) The remaining steps were carried out according to the steps (3), (4) and (5) in example 1.
Finally, the coal-made active coke ozone catalyst containing active components and no auxiliaries is prepared, and the number of the catalyst is the catalyst C.
Example 4
(1) Weighing and mixing bituminous coal, semi-coke and active components according to the mass ratio of 55:40:0, pouring the mixture into a ball mill, grinding the mixture into fine powder with the particle size of more than 200 meshes, and mixing the fine powder, wherein the total mass is 5 kg.
(2) Pouring the powder ground and mixed in the step (1) into a kneader, adding 1kg of water, 0.75kg of asphalt and 0.05kg of sodium hydroxide solution with the concentration of 100mg/L, and kneading for 15 min.
(3) The remaining steps were carried out according to the steps (3), (4) and (5) in example 1.
Finally, the coal-made active coke ozone catalyst containing no active component and containing the auxiliary agent is prepared, and the number of the catalyst is the catalyst D.
Testing the wastewater treatment performance: the ozone catalysts prepared in examples 1, 2, 3 and 4, and commercially available, industrially used activated carbon-based ozone catalyst HH-27 and silicon aluminum-based catalyst HL-17 were evaluated by a wastewater ozone catalytic oxidation test.
The wastewater treatment conditions are as follows: and selecting the effluent of the secondary sedimentation tank after biochemical treatment in a certain steel plant as the sewage to be treated. The catalysts obtained in examples 1 to 4 and the commercially available catalysts HH-27 and HL-17 and a blank control without catalyst were used for wastewater treatment in a fixed bed reactor, respectively. Through determination, the COD concentration of the coking wastewater is about 150mg/L, the pH value is 7.2-8.5, and the chloride ion concentration is about 3000 mg/L.
The inner diameter of the fixed reaction bed is 10cm, and the overall height is 100 cm; the volume of the wastewater is 3L, and the filling volume of the catalyst is 1.5L; the ozone concentration is 60mg/L, the aeration flow is 0.3L/min, the treatment is continuously carried out for 45min under the condition of room temperature, and the COD removal rate is respectively tested. The COD concentration test method refers to the standard of the dichromate determination of chemical oxygen demand of water (HJ 828 + 2017), each group of test samples tests 3 parallel samples, and the average value is taken. The results are shown in Table 1.
TABLE 1 evaluation test results of coking wastewater treatment performance by different catalysts
| Serial number | Condition | 45min COD removal (%) |
| 1 | Catalyst free blank control | 21.2 |
| 2 | Example 1 catalyst A | 82.3 |
| 3 | Example 2 catalyst B | 32.7 |
| 4 | Example 3 catalyst C | 62.1 |
| 5 | Example 4 catalyst D | 27.6 |
| 6 | Active carbon based catalyst HH-27 | 64.5 |
| 7 | Silicon-aluminium base catalyst HL-17 | 57.8 |
As can be seen from table 1:
(1) the test results of the catalysts prepared in the comparative examples 1 to 4 show that the addition of the active component and the auxiliary agent can improve the degradation effect of the catalyst on organic matters, and the analysis reason is probably that the activity, selectivity and stability of the catalyst can be improved and the generation of hydroxyl radicals by ozone catalysis can be promoted by the added active component and the auxiliary agent in the preparation process of the catalyst.
(2) The COD removal rate of the catalyst prepared according to the example 1 is obviously higher than that of commercial catalysts HH-27 and HL-17, which shows that the ozone catalyst of the invention has stronger removal efficiency of refractory organic matters, and the analysis reason is probably that the catalytic specific surface area prepared by the invention is larger, more hydroxyl radicals can be generated by excitation in the same time, and simultaneously, coal is used as a main carrier, so that a certain adsorption effect on the refractory organic matters is generated, the adsorption of the organic matters in water onto the catalyst is accelerated, and the organic matters are reacted with the generated hydroxyl radicals, so that the degradation of the organic matters is accelerated.
And (3) testing the performance of the catalyst: the ozone catalyst prepared in example 1, and commercially available, industrially used activated carbon-based ozone catalyst HH-27 and silicon aluminum-based catalyst HL-17 were subjected to test analysis of indexes such as bulk density, strength, specific surface area, and pore volume.
Measuring the bulk density by adopting a tap density method; measuring the compressive strength of the catalyst by using a strength meter; measuring the specific surface area of the catalyst by adopting a BET method; measuring the total pore volume of the catalyst by adopting a carbon tetrachloride method; the annual attrition rate of the catalyst was determined using an attrition meter.
The test results are shown in Table 2.
TABLE 2 Performance indices of the catalysts
| Item | Example 1 catalyst A | Active carbon based catalyst HH-27 | Silicon-aluminium base catalyst HL-17 |
| Specification (mm) | Round spherulite phi 4-6 | Round spherulite phi 4-6 | Round spherulite phi 6-8 |
| Bulk Density (g/cm)3) | 0.50-0.60 | 0.45-0.55 | 0.6-0.8 |
| Compressive Strength (N/grain) | ≥100 | ≥80 | ≥110 |
| Specific surface area (m)2/g) | 1000-1200 | 1000-1200 | ≥200 |
| Total pore volume (cm)3/g) | ≥0.50 | ≥0.50 | ≥0.40 |
| Annual wear rate | ≤2％ | ≤5％ | ≤1％ |
As can be seen from table 2:
(1) the catalyst prepared in example 1 has better compressive strength, lower annual wear rate and longer service life than the commercial activated carbon-based catalyst HH-27.
(2) The catalyst prepared in example 1 has a lower bulk density, and a larger specific surface area and total pore volume than the commercial silicon-aluminum based catalyst HL-17.
In conclusion, the invention uses coal as raw material, which has lower raw material cost than the silicon-aluminum based catalyst; by adopting a blending preparation process, the active components, the auxiliary agent and the carrier are better combined; by adopting the carbonization activation process, the prepared catalyst has higher compressive strength and lower wear rate than the active carbon-based catalyst, and simultaneously has larger specific surface area, adsorption performance and adsorption capacity.
When the ozone is used for catalyzing, oxidizing and degrading organic matters in the sewage, more organic matters can be adsorbed to the surface of the catalyst, the larger specific surface area can promote more hydroxyl radicals to be generated, the degradation of pollutants is accelerated, and the catalytic oxidation efficiency is higher.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of an active coke-based ozone catalyst prepared from coal is characterized by comprising the following steps: the method comprises the following steps:
(1) grinding: raw coal, semi coke and active components are mixed according to the mass ratio of (30-75): (20-60): (5-10) weighing, grinding into fine powder and mixing; the active component is a mixture of any two or more than two of manganese oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide and cerium oxide;
(2) stirring and kneading: adding water, a binder and an auxiliary agent into the powder ground and mixed in the step (1) for stirring and kneading, wherein the adding amount of the water accounts for 10-25% of the mass of the powder, the adding amount of the binder accounts for 10-30% of the mass of the powder, and the adding amount of the auxiliary agent accounts for 0.1-5% of the mass of the powder;
the auxiliary agent is an alkaline solution containing one or more metal ions;
(3) molding: molding the kneaded material kneaded in the step (2), and airing or drying the obtained molded body until the moisture content is 5-15%;
(4) carbonization and activation: carbonizing and activating the molding material in the step (3);
(5) cooling and screening: and (4) naturally cooling the carbonized and activated catalyst in the step (4), and then sieving to remove powder and fragments to obtain a catalyst finished product.
2. The method for preparing the coal-based active coke-based ozone catalyst according to claim 1, characterized in that: in the step (1), the raw coal is bituminous coal or anthracite; the particle size of the fine powder is more than 200 meshes; when the active components are any two of manganese oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide and cerium oxide, the mass ratio of the two is (1-5): (1-5).
3. The method for preparing the coal-based active coke-based ozone catalyst according to claim 1, characterized in that: in the step (2), the binder is one or more of coal tar, pitch and glycerol; the metal ions comprise potassium, sodium and magnesium; the total metal ion solubility in the alkaline solution is 100-1000 mg/L.
4. The method for preparing the coal-based active coke-based ozone catalyst according to claim 1, characterized in that: in the step (2), the assistant is a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution or a mixed aqueous solution of sodium hydroxide and potassium hydroxide.
5. The method for preparing the coal-based active coke-based ozone catalyst according to claim 1, characterized in that: in the step (2), the kneading time is 10-30 min.
6. The method for preparing the coal-based active coke-based ozone catalyst according to claim 1, characterized in that: the step (3) is as follows: and granulating the kneaded material in a disc granulator to form round balls.
7. The method for preparing the coal-based active coke-based ozone catalyst according to claim 1, characterized in that: the carbonization and activation in the step (4) are as follows: firstly, heating a carbonization activation device to a preset temperature, enabling a molding material to generate a carbonization reaction, maintaining for a period of time, and then heating to activate the molding material; the carbonization is carried out in non-oxidizing atmosphere; the activation is carried out under an atmosphere consisting of a non-oxidizing atmosphere and water vapor.
8. The method for preparing the coal-based active coke-based ozone catalyst according to claim 7, characterized in that: the carbonization heating rate is controlled to be 5-20 ℃/min, the carbonization reaction temperature is 500-800 ℃, and the carbonization reaction time is 0.5-3 h; the activation temperature rate is controlled to be 5-20 ℃/min, the activation reaction temperature is 500-900 ℃, the activation reaction time is 10-120min, and the spraying amount of the water vapor is 5.0-20mL/min/500g of the molding material in the atmosphere consisting of non-oxidizing atmosphere and water vapor.
9. An active coke-based ozone catalyst for coal production is characterized in that: obtained by the production method according to any one of claims 1 to 8.
10. The use of the coal-to-liquids activated coke-based ozone catalyst of claim 9 for the treatment of coking wastewater.
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