CN112093883A - Treatment method of phenol-containing wastewater - Google Patents
Treatment method of phenol-containing wastewater Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 65
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 83
- 239000000843 powder Substances 0.000 claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 25
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 25
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 125
- 238000001816 cooling Methods 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 239000012530 fluid Substances 0.000 claims description 13
- 238000009792 diffusion process Methods 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 12
- 238000000605 extraction Methods 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 48
- 238000012360 testing method Methods 0.000 description 31
- 239000010949 copper Substances 0.000 description 25
- 239000011572 manganese Substances 0.000 description 24
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 17
- 239000012071 phase Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 239000012295 chemical reaction liquid Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 239000011949 solid catalyst Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 7
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 7
- 238000004065 wastewater treatment Methods 0.000 description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004401 flow injection analysis Methods 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- -1 phenol compound Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000725 suspension Substances 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
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Images
Classifications
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- 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
-
- 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
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/002—Construction details of the apparatus
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for treating high-concentration phenol-containing wastewater, which comprises the steps of treating the phenol-containing wastewater by a loop reactor through a powder catalyst; powder type catalyst with Al2O3Is a carrier on which metal active oxides CuO and MnO are loaded2One or two of them, the atomic ratio of metal atoms Cu and Mn is (0-2): 1-3, and the mass ratio of the total mass of the metal active oxide and the carrier is controlled to (15-30): 100. The invention adopts the loop reactor as key process equipment, can treat high-concentration phenol-containing wastewater by one-step reaction to reach the standard and discharge, greatly reduces the process flow compared with the traditional physical extraction, stripping, anaerobic treatment, aerobic treatment and the like, and improves the efficiency.
Description
Technical Field
The invention belongs to the field of phenolic wastewater treatment, and particularly relates to a method for treating phenolic wastewater by catalytic wet oxidation by adopting novel reactor equipment, namely a loop reactor, so that the wastewater reaches the standard and is discharged.
Background
The phenolic substances are generally originated from the petrochemical industry, and the concentration of the phenolic wastewater is gradually increased along with the advance of the production process. High-concentration phenol-containing wastewater not only belongs to toxic and harmful pollutants, but also is difficult to degrade. The traditional treatment methods are divided into physical methods (extraction, adsorption), chemical methods (Fenton reagent method, ozone) and biological methods (activated sludge and enzyme treatment), wherein the physical methods are complex to operate, and the dephenolization efficiency is easily influenced by the operation conditions and is not controlled; the traditional chemical oxidation method has expensive medicament and generates solid waste to cause secondary pollution; the biological method has the problems of poor load impact resistance, low efficiency and the like.
Ozone oxidation in a chemical method is considered to be a cleaner method, but the occupied area is large (an aeration tank is needed), the ozone utilization rate is low, the reality of low ozone utilization rate cannot be changed even though the improved aeration tower occupies a small area and has small investment, and the preparation of ozone needs to consume more energy.
The transition metal outer layer of Mn, Cu, etc. has a d-electron layer structure, and the energy level and shape of the orbitals tend to form complexes, so that Cu2+、Mn2+The transition metal ions are easily bonded to electrons of the organic substance and molecular oxygen to form a complex, and the reactivity of the organic substance molecules with oxygen is improved by electron transfer and ligand transfer.
Loading single-component or multi-component transition metal oxide on porous Al2O3The heterogeneous catalyst on carriers such as activated carbon, gas-phase silicon dioxide and the like is used for treating high-concentration phenol-containing wastewater through catalytic oxidation, the wastewater can be treated at one time and discharged after reaching the standard, the catalyst can be recycled, the cost for treating the high-concentration phenol-containing wastewater is greatly reduced, and the existing heating stirring kettle has low gas-liquid-solid three-phase mass transfer efficiency due to the fact that the wastewater has low viscosity and large surface tension and solid catalyst powder is easy to settle, the reaction needs high temperature and pressure, and the reaction time is long; although the treatment of the phenol-containing wastewater is greatly improved under the acidic condition, the loss of the active center of the catalyst and the corrosion to equipment are caused.
The loop reactor is a novel reactor system and particularly comprises a reaction kettle, a circulating pump, a heat exchanger and a Venturi ejector (mixer). The Venturi ejector can form micron-sized bubbles to be dispersed to a liquid phase in a short time to cause local high gas-liquid mass transfer rate, and turbulent flow and cavitation bubbles formed by jet excitation enable three phases of organic matters and oxygen in the powder catalyst and the aqueous solution to be contacted more fully and uniformly, so that the multiphase reaction speed is accelerated, and the using amount of the catalyst is reduced. (the theoretical mass transfer coefficient of gas-liquid is 10-100 times of that of the common kettle type stirring reactor), thereby improving the efficiency of treating the wastewater. The loop reactor can obtain higher mixing effect with relatively low energy consumption, and the mixed phase is sprayed into the reaction kettle to form good circulation therein, so that the reaction is promoted to be continuously carried out, the reaction effect is improved, the high-concentration phenol-containing wastewater can be effectively decomposed at lower temperature and pressure under a neutral condition (pH is 6.5-7), the catalyst dosage is reduced, and the process time is shortened.
But the metal active oxide is loaded on the porous Al2O3The heterogeneous catalyst on carriers such as activated carbon, gas-phase silicon dioxide, etc. has the bulk density directly influence the distribution of the catalyst at each part of the loop reactor, for example, the loop reactor is adopted for wastewater treatment, aiming at the material characteristics of high-concentration phenol-containing wastewater, in the gas-liquid-solid three-phase reaction, for the loop reactor and a reaction material system with specific design sizes, a certain proportion of solid catalyst is kept in a suspension state in a reaction kettle through liquid/airflow impact, the other part of solid catalyst enters a circulating pipeline from the bottom of the reaction kettle, and finally, the solid catalyst is sprayed into liquid in the reaction kettle again from a Venturi ejector. In the process, factors such as catalyst density and liquid flow injection speed influence the distribution ratio of the catalyst in the reaction kettle and the circulating pipeline. In addition, the liquid in the circulating pipeline contains a certain proportion of solid catalyst, the existence of solid powder influences the dispersion process between the gas phase and the liquid phase, compared with a Venturi ejector with pure gas-liquid two-phase dispersion, the Venturi ejector needs to be further optimally designed (specifically comprising the length of a mixing section, the length of a diffusion section, an opening angle and the like), and the density of the solid powder in a specified reaction material system needs to be fully considered for the Venturi ejectorThe area in the reactor and the gas-liquid-solid three-phase mass transfer process in the reaction kettle.
Disclosure of Invention
The invention provides a method for treating high-concentration phenol-containing wastewater by adopting a novel reactor system, namely a loop reactor.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for treating high-concentration phenol-containing wastewater uses a powder catalyst to treat the phenol-containing wastewater through a loop reactor; powder type catalyst with Al2O3Is a carrier on which metal active oxides CuO and MnO are loaded2One or two of them, the atomic ratio of metal atoms Cu and Mn is (0-2): 1-3, and the mass ratio of the total mass of the metal active oxide and the carrier is controlled to (15-30): 100.
Wherein the COD concentration of the phenolic wastewater to be treated is 1500 mg/L-4000 mg/L; the dosage of the catalyst is 5-40 g/3.5L of wastewater.
Further preferably, the amount of the catalyst used is 2 to 8 times (mass ratio) the total content of the phenolic compounds in the wastewater.
The catalyst is prepared by the following method:
taking Al which is ground after being dried at about 105 DEG C2O3Putting the powder into a reaction container, adding a mixed aqueous solution of copper nitrate, manganese nitrate or copper nitrate and manganese nitrate under a vacuum condition, stirring and evaporating in a water bath at about 90 ℃ (90-95 ℃), drying, grinding, putting into a tubular furnace, heating to 550-600 ℃, keeping the temperature for about 4 hours, and cooling to room temperature to obtain the powder catalyst.
The method for treating the phenol-containing wastewater comprises the following specific steps:
taking high-concentration phenol-containing wastewater, adding the powder catalyst with COD concentration of about 3000mg/L (2900 mg/L-3060 mg/L), uniformly mixing, adding the mixture into a reaction kettle of a loop reactor, introducing air to control the reaction pressure to be 0.5 MPa-2 MPa for catalytic oxidation, controlling the reaction temperature to be 60-120 ℃ and controlling the reaction time to be 0.5-1.5 h.
In some embodiments, the amount of the powder catalyst is preferably 20 to 40g/3.5L of wastewater (further, the amount of the catalyst is 4 to 8 times the amount of the phenolic compounds in the phenol-containing wastewater). Wherein the atomic ratio of metal atoms Cu to Mn in the powder catalyst is (0-2): 1-2, and the mass ratio of the total mass of the metal active oxides to the carrier is controlled to be (20-25): 100.
In some examples, it is more preferable that the amount of the powder type catalyst is 30g/3.5L of the waste water (further, the amount of the catalyst is 6 times the amount of the phenol compound in the phenol-containing waste water). Wherein the powder catalyst comprises Cu and Mn in an atomic ratio of 1:2, the mass ratio of the active metal oxide to the carrier is 25:100, and the bulk density is 1.132g/cm by a Scott densitometer test3。
Among them, preferable values for the reaction parameters are: the reaction temperature is controlled at 90 ℃, the reaction pressure is 1.2MPa, and the reaction time is 1 h.
Because the solid powder catalyst adopted by the invention has larger influence on the process of gas-liquid phase dispersion in the reaction process, the Venturi ejector adopted by the reaction is optimized on the basis. The bulk density of the powder catalyst is 0.8-1.6 g/cm3In the loop reactor designed by the invention, the inner diameter of the opening of the inlet section of the Venturi ejector is as follows: nozzle bore diameter: the inner diameter of the closed air chamber: length of mixed section: the ratio of the length of the diffusion section is 34: (1-5): (2-6): (15-55): (800-1600) and the opening angle of the diffusion section is 15-35 degrees; and controlling the linear velocity of the fluid at the nozzle of the Venturi ejector to be 60-100 m/s in the reaction process.
In some embodiments, it is preferred that the inlet section opening internal diameter of the venturi ejector in the loop reactor is: nozzle bore diameter: the inner diameter of the closed air chamber: length of mixed section: the ratio of the length of the diffusion section is 34: 4: 6: 55: 1000, the opening angle of the diffusion section is 20 degrees; the linear velocity of the fluid at the nozzle of the venturi eductor during the reaction was 80 m/s.
The invention focuses on the relation between the density of the solid catalyst and the design size of the Venturi ejector aiming at the material characteristics of the high-concentration phenol-containing wastewater. In the gas-liquid-solid three-phase reaction, for a loop reactor and a reaction material system with specific design sizes, a certain proportion of solid catalyst is kept in a suspended state in a reaction kettle through liquid/gas flow impact, and the other part of solid catalyst enters a circulating pipeline from the bottom of the reaction kettle and is finally sprayed into liquid in the reaction kettle again from a Venturi ejector. In the process, factors such as catalyst density and liquid flow injection speed influence the distribution ratio of the catalyst in the reaction kettle and the circulating pipeline. In addition, the liquid in the circulating pipeline contains a certain proportion of solid catalyst, the existence of solid powder influences the gas-liquid two-phase dispersion process, compared with a pure gas-liquid two-phase dispersion Venturi ejector, the Venturi ejector needs to be further optimally designed (specifically comprising the length of a mixing section, the length of a diffusion section, an opening angle and the like), and the influence of the density of the solid powder in a specified reaction material system on the gas-liquid-solid three-phase mass transfer process in the Venturi ejector and in a reaction kettle is fully considered.
In addition, the technology for treating the wastewater only uses air as an air source instead of oxygen, thereby being safe in production, reducing the reaction temperature and pressure, shortening the reaction time and improving the efficiency of treating the high-concentration phenol-containing wastewater.
Compared with the prior art, the invention has the following advantages:
1. the loop reactor is adopted as key process equipment, high-concentration phenol-containing wastewater can be treated by one-step reaction and discharged after reaching the standard, the process flow is greatly reduced compared with the traditional physical extraction-stripping-anaerobic-aerobic treatment and the like, and the efficiency is improved.
2. The Venturi ejector designed aiming at the characteristics of low wastewater viscosity, large surface tension and the like can form micron-sized bubbles to be dispersed to a liquid phase in a short time, so that the local high gas-liquid mass transfer rate is caused, and turbulent flow and cavitation bubbles formed by jet excitation fully contact solid catalyst powder, liquid phase organic matter molecules and oxygen in a gas phase, so that the reaction speed of wastewater oxidation is accelerated, and the using amount of a catalyst is reduced.
3. The invention only adopts the transition metal powder type catalyst and the simple and easily obtained compressed air, and does not need the pure oxygen environment and the acid condition under the high temperature and the high pressure of the traditional reaction kettle, thereby improving the safety factor and reducing the loss of the catalyst and the corrosion to equipment.
Drawings
FIG. 1 is a schematic view showing the structure of a loop reactor for treating phenol-containing wastewater according to the present invention;
FIG. 2 is a schematic diagram of the venturi eductor of FIG. 1 according to the present invention.
In the figure, 1-a reaction kettle, 2-a Venturi ejector, 3-a heat exchanger, 4-a circulating pump and 5-a gas circulating pipe; 6-inlet section, 7-mixing section, 8-diffusion section, 9-nozzle, 10-air chamber.
Detailed Description
The invention is described in detail below with reference to the figures and the specific embodiments.
As shown in figure 1, the method for treating the high-concentration phenol-containing wastewater adopts a loop reactor to carry out batch reaction. The loop reactor comprises a reaction kettle 1, a circulating pump 4, a heat exchanger 3 and a Venturi ejector 2.
When the reactor works, the circulating pump is started. The reaction liquid circulates in the loop at a large flow rate, the venturi ejector 2 ejects at a high speed, and negative pressure is formed at the working nozzle, so that gas (air) is sucked into the venturi ejector. One side of the top of the reaction kettle 1 is provided with a branch pipe which is connected with an air inlet and can form air circuit circulation locally. The Venturi ejector forms tiny bubbles with large specific surface area, gas-liquid-solid three-phase contact is increased, and the reaction speed is accelerated. The lower end of the Venturi ejector is positioned below the liquid level, and the gas-liquid-solid mixed material and the materials in the reaction kettle are impacted, so that the effect of promoting dispersion and mixing is achieved, and the reaction is promoted to further proceed. The material enters the heat exchanger from the bottom end of the reaction kettle through the circulating pump 4 and enters the Venturi ejector 2 from the top end of the reaction kettle 1. The heat exchanger 3 removes or provides heat released or absorbed in the reaction process, and controls the fluctuation of the reaction temperature to +/-1 ℃. And (3) gradually reducing the reactants and gradually increasing the products along with the reaction, and discharging the reaction products from the bottom end of the reaction kettle after the reaction is completely finished.
The heat exchanger in this patent can adopt tubular heat exchanger or plate heat exchanger.
Aiming at the catalytic oxidation of the wastewater under the condition of certain pressure and temperature, the design structure size of the Venturi ejector greatly influences the effect of mutual dispersion and contact among reaction substances, thereby finally influencing the efficiency of wastewater treatment. Referring to fig. 2, the venturi ejector 2 of the present invention is specifically composed of a plurality of portions, such as a reducer-shaped inlet section 6, a nozzle 9, a mixing section 7, a diffuser section 8, and a gas chamber 10. As shown in FIG. 1, a gas circulation pipe 5 is provided at the side of the gas chamber 10 and connected to the top of the reaction vessel 1 to provide a gas circulation space in a local region.
In the initial stage of wastewater treatment, analytically pure phenol-hydroquinone is dissolved in secondary distilled water to simulate high-concentration phenol-containing wastewater, the COD of the solution is about 3000mg/L, a powder catalyst is added, and the mixture is uniformly mixed and added into a reaction kettle of a loop reactor through a feed inlet (the pH is not required to be adjusted to be acidic). Air is introduced into the reactor through the air inlet to a certain pressure, the circulating pump 4 is started to enable the liquid in the kettle to slowly flow, and the circulating pump 4 is adjusted until the flow rate reaches a certain value and is recorded as the reaction starting time.
When the reaction is finished, the flow rate of the circulating pump 4 is immediately reduced and the temperature is rapidly reduced to the room temperature (the temperature reduction time is about 15 min). And (3) emptying the gas in the kettle, discharging liquid in the kettle, filtering and separating, and testing COD (chemical oxygen demand) of the liquid by adopting a national environmental protection standard HJ 828-2017 potassium dichromate method of the people's republic of China.
Catalyst preparation examples
1. Experimental materials
Cu(NO3)2·2.5H2O (national drug group chemical agents Co., Ltd A.R.)
Mn(NO3)2Aqueous solution (50% mass concentration of national drug group chemical Co., Ltd.)
The alumina carrier is from Jinling petrochemical alkylbenzene factory, has a diameter of 1-2mm, and is ground into powder for use, SBET＝211m2G, pore volume 0.9cm3The pore diameter is 15.1nm, and the bulk density of the carrier powder is 0.85g/cm as measured by a Scott densitometer3。
Fumed silica support from Wacker' S Germany, specific surface area SBET＝150m2(hydrophilic type) and a bulk density of 0.05g/cm3。
2. Preparation process
Cu (NO) to be metered3)2·2.5H2O (national chemical group chemical reagent, Inc. A.R.) was dissolved in a predetermined amount of deionized water to prepare a solution having a Cu atomic concentration of 0.15 mol/L.
Catalyst preparation example A
Weighing and metering Al2O3Adding the powder into a custom glass container, vacuumizing for 1h, and adding a certain volume of the copper nitrate solution (Al)2O3The addition amount of the powder and the addition amount of the copper nitrate solution are represented by the following formula: al (Al)2O3The mass ratio of (A) is controlled to be CuO: al (Al)2O3Is that the ratio of 15: 100, respectively; stirring and evaporating in a water bath at 95 ℃ to dryness, and air drying at 110 ℃ for 5 h. Grinding the sample, placing the sample in a tube furnace, heating to 550 ℃ at the speed of 3 ℃/min, keeping the temperature for 4h, and cooling to room temperature to obtain CuO/Al2O3The powder catalyst has a bulk density of 0.874g/cm as measured by Scott densitometer3。
Catalyst preparation example B
Weighing and metering Al2O3Adding the powder into a custom-made glass container, vacuumizing for 1h, and adding a certain volume of the manganese nitrate solution (Al)2O3The addition amount of the powder and the addition amount of the manganese nitrate solution are MnO2：Al2O3The mass ratio of (A) is measured and controlled to MnO2：Al2O3Is 20:100, respectively; stirring and evaporating in a water bath at 95 ℃ to dryness, and air drying at 110 ℃ for 5 h. Grinding the sample, placing the ground sample in a tube furnace, heating the sample to 550 ℃ at the speed of 3 ℃/min, keeping the temperature for 4 hours, and cooling the sample to room temperature to obtain MnO2/Al2O3The powder catalyst has a bulk density of 0.853g/cm as measured by Scott densitometer3。
Catalyst preparation example C
Weighing and metering Al2O3Adding the powder into a custom glass container, vacuumizing for 1h, and measuring 0.15mol/L Cu (NO)3)2Solution with 50% Mn (NO)3)2Solution, added together, with control of the atomic ratio of Cu to Mn, and active oxidation of the metal according to experimental requirementsThe mass ratio of the material to the carrier of the aluminum oxide is dried by distillation in a water bath at 95 ℃ and air-dried for 5h at 110 ℃. Grinding the sample, placing the ground sample in a tube furnace, heating to 600 ℃ at the speed of 3 ℃/min, keeping the temperature for 4 hours, and cooling to room temperature to obtain CuO-MnO2/Al2O3A powder catalyst.
Catalyst preparation example D
Preparation of CuO-MnO by Replacing the Supported fumed silica according to the method of catalyst preparation example C2/SiO2A powder catalyst.
Examples of wastewater treatment
Example 1
To a 5L loop reactor (reactor volume 5L), 3.5L of simulated high concentration phenol-containing wastewater (2.5 g each of phenol and hydroquinone, COD 3053mg/L) was charged, and CuO/Al prepared in catalyst preparation example A was added2O3Catalyst powder (bulk density 0.874 g/cm)3)15g, introducing air into the reactor through an air inlet until the system pressure is 0.5MPa, starting a circulating pump to enable liquid in the reactor to slowly flow, heating to a preset reaction temperature of 60 ℃ (the heating time is about 15min), adjusting the circulating pump to 4 to a flow speed of 60m/s, and recording as the reaction starting time. In the reaction process, the temperature of the connecting reaction kettle is controlled to be 60 +/-1 ℃. And (4) reacting for 0.5h, immediately reducing the flow rate of the circulating pump 4, rapidly cooling to room temperature (the cooling time is about 15min), and taking the liquid after emptying to filter and test COD.
During the reaction, the linear velocity of the fluid at the nozzle of the Venturi ejector is controlled to be 60m/s, and the detailed design size is specifically that the inner diameter D1 of the opening of the inlet section: nozzle inner diameter D2: air chamber closing-in inner diameter D3: mixing segment length L1: the ratio of diffuser length L2 is 34: 2.5: 4: 35: 900 and the diffuser section opening angle alpha is 15 deg., as shown in fig. 2. The lowermost end of the venturi jet is inserted below the reaction liquid level. COD removal rate of the filtered liquid after reaction is 22.5 percent by testing COD, and Cu loss of the solution is less than 0.5PPm by ICP test.
Example 2
Into a 5L loop reactor (reactor volume 5L), 3.5L of simulated high concentration phenol-containing wastewater (2.5 g each of phenol and hydroquinone, COD 3053mg/L) was charged, and the catalyst prepared in preparation example B was addedTo MnO of2/Al2O3Catalyst powder (bulk density 0.853 g/cm)3) And 40g, introducing air into the reactor through an air inlet until the system pressure is 0.5MPa, starting a circulating pump to enable liquid in the reactor to slowly flow, heating to a preset reaction temperature of 120 ℃ (the heating time is about 15min), adjusting the circulating pump to 4-flow speed of 100m/s, and recording as the reaction starting time. In the reaction process, the temperature of the connecting reaction kettle is controlled to be 120 +/-1 ℃. And reacting for 1.5h, immediately reducing the flow rate of the circulating pump 4, rapidly cooling to room temperature (the cooling time is about 15min), and taking the liquid after emptying to filter and test COD.
During the reaction process, the linear velocity of the fluid at the nozzle of the Venturi ejector is controlled to be 100m/s, and the detailed design size is specifically that the inner diameter D1 of the opening of the inlet section: nozzle inner diameter D2: air chamber closing-in inner diameter D3: mixing segment length L1: the ratio of diffuser length L2 is 34: 2: 4.5: 50: 1600 and the diffuser section opening angle alpha is 35 deg., as shown in fig. 2. The lowermost end of the venturi jet is inserted below the reaction liquid level. COD removal rate of the filtered liquid after reaction is 88.6 percent by testing COD, and Mn loss of the solution is less than 0.5PPm by ICP test.
Example 3
To a 5L loop reactor (reactor volume 5L), 3.5L of simulated high concentration phenol-containing wastewater (2.5 g each of phenol and hydroquinone, COD 3053mg/L) was charged, and CuO-MnO prepared by the method of catalyst preparation example C was added2/Al2O3Powder catalyst (bulk density 0.976 g/cm)3)20g, wherein the atomic ratio of the metal active center Cu atom to Mn atom is 1: 1, the mass ratio of the metal active oxide to the carrier is 20: 100. Introducing air into the reactor through the air inlet until the system pressure is 2MPa, starting the circulating pump to enable the liquid in the reactor to slowly flow, heating to the preset reaction temperature of 100 ℃ (the heating time is about 15min), adjusting the circulating pump to 4-flow rate of 90m/s, and recording as the reaction starting time. In the reaction process, the temperature of the connecting reaction kettle is controlled to be 100 +/-1 ℃. And (4) reacting for 1h, immediately reducing the flow rate of the circulating pump 4, rapidly cooling to room temperature (the cooling time is about 15min), and taking the liquid after emptying to filter and test COD.
In the reaction process, the linear velocity of the fluid at the nozzle of the Venturi ejector is controlled to be 90m/s, and the detailed design size is specifically that the inner diameter D1 of the opening of the inlet section: nozzle inner diameter D2: air chamber closing-in inner diameter D3: mixing segment length L1: the ratio of diffuser length L2 is 34: 3.5: 6: 45: 1400, the diffuser section opening angle α is 25 °, as shown in fig. 2. The lowermost end of the venturi jet is inserted below the reaction liquid level. COD removal rate of the filtered liquid after reaction is 83.3 percent by testing COD, Cu loss of the solution is less than 0.5PPm by ICP test, and Mn loss is less than 0.5 PPm.
Example 4
To a 5L loop reactor (reactor volume 5L), 3.5L of simulated high concentration phenol-containing wastewater (2.5 g each of phenol and hydroquinone, COD 3053mg/L) was charged, and CuO-MnO prepared by the method of catalyst preparation example C was added2/Al2O3Powder catalyst (bulk density 1.132 g/cm)3)30g, wherein the atomic ratio of the metal active center Cu atom to Mn atom is 1: and 2, the mass ratio of the metal active oxide to the carrier is 25:100, air is introduced into the reactor through the air inlet until the system pressure is 1.2MPa, the circulating pump is started to enable the liquid in the reactor to slowly flow, the temperature is raised to a preset reaction temperature of 90 ℃ (the temperature raising time is about 15min), the circulating pump is adjusted to be 4 to the flow rate of 80m/s, and the reaction starting time is recorded. In the reaction process, the temperature of the connecting reaction kettle is controlled to be 90 +/-1 ℃. And (4) reacting for 1h, immediately reducing the flow rate of the circulating pump 4, rapidly cooling to room temperature (the cooling time is about 15min), and taking the liquid after emptying to filter and test COD.
In the reaction process, the linear velocity of the fluid at the nozzle of the Venturi ejector is controlled to be 80m/s, and the detailed design size is specifically that the inner diameter D1 of the opening of the inlet section: nozzle inner diameter D2: air chamber closing-in inner diameter D3: mixing segment length L1: the ratio of diffuser length L2 is 34: 4: 6: 55: 1000 with the diffuser section opening angle alpha at 20 deg., as shown in fig. 2. The lowermost end of the venturi jet is inserted below the reaction liquid level. COD removal rate of the filtered liquid after reaction is 99.6 percent by testing COD, Cu loss of the solution is less than 0.5PPm by ICP test, and Mn loss is less than 0.5 PPm.
Example 5
To a 5L loop reactor (reactor volume 5L), 3.5L of simulated high concentration phenol-containing wastewater (2.5 g each of phenol and hydroquinone, COD 3053mg/L) was charged, and CuO-MnO prepared by the method of catalyst preparation example C was added2/Al2O3Powder catalyst (bulk density 1.585 g/cm)3)25g, wherein the metal active center Cu atom to Mn atomic ratio is 1: and 3, the mass ratio of the metal active oxide to the carrier is 30:100, air is introduced into the reactor through the air inlet until the system pressure is 1.2MPa, the circulating pump is started to enable the liquid in the reactor to slowly flow, the temperature is raised to the preset reaction temperature of 90 ℃ (the temperature raising time is about 15min), the circulating pump is adjusted to be 4 to the flow rate of 80m/s, and the reaction starting time is recorded. In the reaction process, the temperature of the connecting reaction kettle is controlled to be 90 +/-1 ℃. And (4) reacting for 1h, immediately reducing the flow rate of the circulating pump 4, rapidly cooling to room temperature (the cooling time is about 15min), and taking the liquid after emptying to filter and test COD.
In the reaction process, the linear velocity of the fluid at the nozzle of the Venturi ejector is controlled to be 80m/s, and the detailed design size is specifically that the inner diameter D1 of the opening of the inlet section: nozzle inner diameter D2: air chamber closing-in inner diameter D3: mixing segment length L1: the ratio of diffuser length L2 is 34: 2.5: 4: 30: the diffuser section opening angle α is 20 ° as shown in fig. 2. The lowermost end of the venturi jet is inserted below the reaction liquid level. COD removal rate of the filtered liquid after reaction is 63.4 percent by testing COD, Cu loss of the solution is less than 0.5PPm by ICP test, and Mn loss is less than 0.5 PPm.
It can be seen from examples 1 to 5 that the single-component copper oxide catalyst is not as effective as the catalyst added with Mn element, and the bulk density of the catalyst has a great influence on the reaction, and for a specific venturi reactor, it is not preferable that the particle size of the catalyst is smaller, and it is particularly important to select an appropriate catalyst and the particle size of the catalyst for the feature of low viscosity of wastewater.
Example 6
To a 5L loop reactor (reactor volume 5L), 3.5L of simulated high concentration phenol-containing wastewater (2.5 g each of phenol and hydroquinone, COD 3053mg/L) was charged, and CuO-MnO prepared by the method of catalyst preparation example C was added2/Al2O3Catalyst powder (bulk density 1.596 g/cm)3)25g, wherein the metal active center Cu atom to Mn atomic ratio is 2: 3, the mass ratio of the metal active oxide to the carrier is 30:100, air is introduced into the reactor through an air inlet until the system pressure is 1.5MPa, and a circulating pump is started to ensure that the liquid in the reactor is in a liquid stateThe body slowly flows, the temperature is raised to the preset reaction temperature of 90 ℃ (the temperature rise time is about 15min), the circulating pump 4 is adjusted to the flow rate of 80m/s, and the reaction start time is recorded. In the reaction process, the temperature of the connecting reaction kettle is controlled to be 90 +/-1 ℃. And (4) reacting for 1h, immediately reducing the flow rate of the circulating pump 4, rapidly cooling to room temperature (the cooling time is about 15min), and taking the liquid after emptying to filter and test COD.
In the reaction process, the linear velocity of the fluid at the nozzle of the Venturi ejector is controlled to be 80m/s, and the detailed design size is specifically that the inner diameter D1 of the opening of the inlet section: nozzle inner diameter D2: air chamber closing-in inner diameter D3: mixing segment length L1: the ratio of diffuser length L2 is 34: 2: 6: 50: the diffuser section opening angle α is 20 ° as shown in fig. 2 at 1500. The lowermost end of the venturi jet is inserted below the reaction liquid level. COD removal rate of the filtered liquid after reaction is 77.9 percent by testing COD, Cu loss of the solution is less than 0.5PPm by ICP test, and Mn loss is less than 0.5 PPm.
Example 7
To a 5L loop reactor (reactor volume 5L), 3.5L of simulated high concentration phenol-containing wastewater (2.5 g each of phenol and hydroquinone, COD 3053mg/L) was charged, and CuO-MnO prepared by the method of catalyst preparation example C was added2/Al2O3Catalyst powder (bulk density 1.153 g/cm)3)25g, wherein the metal active center Cu atom to Mn atomic ratio is 2: 1, the mass ratio of the metal active oxide to the carrier is 25:100, air is introduced into the reactor through an air inlet until the system pressure is 1MPa, a circulating pump is started to enable liquid in the reactor to slowly flow, the temperature is raised to 90 ℃ which is the preset reaction temperature (the temperature rise time is about 15min), the circulating pump is adjusted to 4 to 70m/s of flow speed, and the flow speed is recorded as the reaction start time. In the reaction process, the temperature of the connecting reaction kettle is controlled to be 80 +/-1 ℃. Reacting for 80min, immediately reducing the flow rate of the circulating pump 4, rapidly cooling to room temperature (the cooling time is about 15min), and taking the liquid after emptying to filter and test COD.
During the reaction, the linear velocity of the fluid at the nozzle of the Venturi ejector is controlled to be 70m/s, and the detailed design size is specifically that the inner diameter D1 of the opening of the inlet section: nozzle inner diameter D2: air chamber closing-in inner diameter D3: mixing segment length L1: the ratio of diffuser length L2 is 34: 1: 6: 20: 1050, the diffuser section opening angle α is 30, as shown in fig. 2. The lowermost end of the venturi jet is inserted below the reaction liquid level. COD removal rate of the filtered liquid after reaction is 91.5 percent by testing COD, Cu loss of the solution is less than 0.5PPm by ICP test, and Mn loss is less than 0.5 PPm.
Example 8
To a 5L loop reactor (reactor volume 5L), 3.5L of simulated lower concentration phenol-containing wastewater (1.25 g each of phenol and hydroquinone, COD 1536mg/L) was charged, and CuO-MnO prepared by the method of catalyst preparation example C was added2/Al2O3Powder catalyst (bulk density 1.132 g/cm)3)5g, wherein the atomic ratio of the metal active center Cu atom to Mn atom is 1: and 2, the mass ratio of the metal active oxide to the carrier is 25:100, air is introduced into the reactor through the air inlet until the system pressure is 1.2MPa, the circulating pump is started to enable the liquid in the reactor to slowly flow, the temperature is raised to a preset reaction temperature of 90 ℃ (the temperature raising time is about 15min), the circulating pump is adjusted to be 4 to the flow rate of 80m/s, and the reaction starting time is recorded. In the reaction process, the temperature of the connecting reaction kettle is controlled to be 90 +/-1 ℃. And (4) reacting for 1h, immediately reducing the flow rate of the circulating pump 4, rapidly cooling to room temperature (the cooling time is about 15min), and taking the liquid after emptying to filter and test COD.
In the reaction process, the linear velocity of the fluid at the nozzle of the Venturi ejector is controlled to be 80m/s, and the detailed design size is specifically that the inner diameter D1 of the opening of the inlet section: nozzle inner diameter D2: air chamber closing-in inner diameter D3: mixing segment length L1: the ratio of diffuser length L2 is 34: 4: 6: 55: 1000 with the diffuser section opening angle alpha at 20 deg., as shown in fig. 2. The lowermost end of the venturi jet is inserted below the reaction liquid level. COD removal rate of the filtered liquid after reaction is 96.7 percent by testing COD, Cu loss of the solution is less than 0.5PPm by ICP test, and Mn loss is less than 0.5 PPm.
As can be seen from example 8, the design specifications of the Venturi ejector according to the invention and the CuO-MnO according to the invention were used2/Al2O3The powder catalyst also has excellent COD removal rate for the phenolic wastewater with lower concentration.
COMPARATIVE EXAMPLE 1 (Autoclave)
A2L reaction kettle is added with 1.2L simulated high-concentration phenol-containing wastewater (0.85 g of phenol and hydroquinone respectively, and the COD is 3027mg/L) to be added into the reaction kettleCuO-MnO of 42/Al2O3Powder catalyst (bulk density 1.132 g/cm)3)10.2g, wherein the metal active center Cu atom to Mn atom ratio is 1:2, the mass ratio of the metal active oxide to the carrier is 25:100, air is introduced until the pressure is 1.5MPa, stirring and heating are carried out until the temperature is 90 ℃, the rotation speed is adjusted to 700rpm, the time is 1h, stirring is stopped, cooling is carried out, pressure is relieved, sampling is carried out, and the COD conversion rate is 23.3%.
As can be seen from the test results of example 4 and comparative example 1, the COD conversion rate of the reaction using the same catalyst in the form of an autoclave is low, the reaction is poor, and the effect of wastewater treatment using a loop reactor is obviously better than that of wastewater treatment using an autoclave.
Comparative example 2
To a 5L loop reactor (reactor volume 5L), 3.5L of simulated high concentration phenol-containing wastewater (2.5 g each of phenol and hydroquinone, COD 3053mg/L) was charged, and CuO-MnO prepared by the method of catalyst preparation example D was added2/SiO230g of a powder catalyst, wherein the atomic ratio of a metal active center Cu atom to Mn is 1:2, the mass ratio of the metal active oxide to the carrier is 25:100, and CuO-MnO is2/SiO2The bulk density of the powder catalyst was 0.402g/cm3Introducing air into the reactor through the air inlet until the system pressure is 1.2MPa, starting the circulating pump to enable the liquid in the reactor to slowly flow, heating to the preset reaction temperature of 90 ℃ (the heating time is about 15min), adjusting the circulating pump to 4-flow rate of 80m/s, and recording as the reaction starting time. In the reaction process, the temperature of the connecting reaction kettle is controlled to be 90 +/-1 ℃. And (4) reacting for 1h, immediately reducing the flow rate of the circulating pump 4, rapidly cooling to room temperature (the cooling time is about 15min), and taking the liquid after emptying to filter and test COD.
In the reaction process, the linear velocity of the fluid at the nozzle of the Venturi ejector is controlled to be 80m/s, and the detailed design size is specifically that the inner diameter D1 of the opening of the inlet section: nozzle inner diameter D2: air chamber closing-in inner diameter D3: mixing segment length L1: the ratio of diffuser length L2 is 34: 4: 6: 55: 1000 with the diffuser section opening angle alpha at 20 deg., as shown in fig. 2. The lowermost end of the venturi jet is inserted below the reaction liquid level. COD removal rate of the filtered liquid after reaction is tested to obtain 68.1 percent, Cu loss of the solution is less than 0.5PPm through ICP test, and Mn loss is less than 0.5 PPm.
From the test results of example 4 and comparative example 2, it can be seen that the bulk density of the catalyst is complementary to the venturi design, and the appropriate bulk density and venturi design can accelerate the reaction. Under the same venturi design, the treatment effect of the waste water by adopting the catalysts with different bulk densities has obvious difference.
Application examples
Taking phenol-containing wastewater which is not treated in a petrochemical plant and contains phenol, cresol, benzenediol and the like as main pollutants (COD is about 2600mg/L, pH is 6.3)3.5L, adding CuO-MnO which is prepared by the catalyst preparation example C2/Al2O3Catalyst powder 25g (bulk density 1.132 g/cm)3) Wherein the atomic ratio of Cu atoms to Mn atoms of the metal active center is 1:2, the mass ratio of the metal active oxide to the carrier is 25:100, and the specification and the size of the Venturi ejector are the same as those of the embodiment 4. Introducing air into the reactor through the air inlet until the system pressure is 1.2MPa, starting the circulating pump to enable the liquid in the reactor to slowly flow, heating to the preset reaction temperature of 90 ℃ (the heating time is about 15min), adjusting the circulating pump to 4-flow rate of 80m/s, and recording as the reaction starting time. In the reaction process, the temperature of the connecting reaction kettle is controlled to be 90 +/-1 ℃. And (3) reacting for 1h, immediately reducing the flow rate of the circulating pump 4, rapidly cooling to room temperature (the cooling time is about 15min), emptying, taking liquid, filtering and testing COD, and obtaining the COD conversion rate of 99.9%.
Claims (9)
1. The treatment method of the phenolic wastewater is characterized in that the phenolic wastewater is treated by a powder catalyst through a loop reactor; the powder type catalyst is Al2O3Is a carrier on which metal active oxides CuO and MnO are loaded2One or two of them, the atomic ratio of metal atoms Cu and Mn is (0-2): 1-3, and the mass ratio of the total mass of the metal active oxide and the carrier is controlled to (15-30): 100.
2. The method according to claim 1, wherein the COD concentration of the phenol-containing wastewater is 1500mg/L to 4000 mg/L; the dosage of the catalyst is 5-40 g/3.5L of wastewater.
3. The method for treating phenol-containing wastewater according to claim 2, comprising the steps of: adding the phenolic wastewater into the powder catalyst, uniformly mixing, adding into a reaction kettle of a loop reactor, introducing air to control the reaction pressure to be 0.5-2 MPa for catalytic oxidation, controlling the reaction temperature to be 60-120 ℃, and controlling the reaction time to be 0.5-1.5 h.
4. The method for treating phenol-containing wastewater according to claim 3, wherein the bulk density of the powdery catalyst is 0.8 to 1.6g/cm3(ii) a The inner diameter of the inlet section opening of the venturi ejector in the loop reactor is as follows: nozzle bore diameter: the inner diameter of the closed air chamber: length of mixed section: the ratio of the length of the diffusion section is 34: (1-5): (2-6): (15-55): (800-1600) and the opening angle of the diffusion section is 15-35 degrees; and controlling the linear velocity of the fluid at the nozzle of the Venturi ejector to be 60-100 m/s in the reaction process.
5. The method for treating phenol-containing wastewater according to claim 4, wherein said powdery catalyst is prepared by: taking the dried and ground Al2O3Putting the powder into a reaction container, adding the nitrate aqueous solution of the metal active oxide under the vacuum condition, heating in a water bath, stirring and evaporating to dryness, drying, grinding, putting into a tubular furnace, heating to 550-600 ℃, keeping the temperature for 4 hours, and cooling to room temperature to obtain the powder catalyst.
6. The method according to claim 5, wherein the COD concentration of the phenol-containing wastewater is 2900mg/L to 3060 mg/L; the dosage of the catalyst is 20-40 g/3.5L of wastewater.
7. The method for treating phenol-containing wastewater according to claim 5 or 6, wherein the atomic ratio of metal atoms Cu to Mn in the powder catalyst is (0-2): 1-2, and the mass ratio of the total mass of the metal active oxides to the carrier is controlled to (20-25): 100.
8. The method according to claim 7, wherein the powdery catalyst is Al2O3Is a carrier on which metal active oxides CuO and MnO are loaded2The atomic ratio of metal atoms Cu to Mn is 1:2, and the mass ratio of the total mass of the metal active oxides to the carrier is 25: 100.
9. The method for treating phenol-containing wastewater according to any one of claims 4 to 8, wherein the inner diameter of the inlet section opening of the venturi ejector in the loop reactor is as follows: nozzle bore diameter: the inner diameter of the closed air chamber: length of mixed section: the ratio of the length of the diffusion section is 34: 4: 6: 55: 1000, the opening angle of the diffusion section is 20 degrees; and controlling the linear velocity of the fluid at the nozzle of the Venturi ejector to be 80m/s in the reaction process.
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| CN107010709A (en) * | 2017-05-27 | 2017-08-04 | 南京工业大学 | The purification method of high-concentration phenolic wastewater during a kind of neighbour/Process of Hydroquinone Production |
| CN111330573A (en) * | 2020-04-10 | 2020-06-26 | 江苏诺盟化工有限公司 | Catalyst for preparing 1, 3-propylene glycol from glycerol and method for preparing 1, 3-propylene glycol by adopting loop reactor |
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