CN110386655B - Method for treating industrial difficult-to-biochemically-treated sewage based on continuous free radical generator - Google Patents
Method for treating industrial difficult-to-biochemically-treated sewage based on continuous free radical generator Download PDFInfo
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- 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
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- 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
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
Abstract
The invention provides a method for treating industrial wastewater difficult to be biochemically treated based on a continuous free radical generator, which adopts air as an oxidant, has small occupied area of equipment, low long-term operation cost and safe and controllable process; the method has the advantages of convenience, practicability, high catalyst reaction activity, thorough removal of pollutants, no generation of toxic and harmful gases, no generation of sludge and no secondary pollution in the sewage treatment process, the COD8000- & ltSUB & gt 100000mg/L of the inlet sewage, direct discharge or biochemical treatment of the outlet water, the highest CODcr removal rate of more than 95 percent, and the treated BOD5/CODcr > 0.3.
Description
Technical Field
The invention relates to the field of sewage treatment, in particular to a method for treating industrial biochemical-difficult sewage based on a continuous free radical generator.
Background
Since the production of antibiotics begins in the early 50 s of the 20 th century, the yield of the antibiotics is increased year by year, and the antibiotics become one of the major antibiotic drug production countries in the world. In the production process of antibiotics in China, the problems of complex components, difficult treatment and the like of production sewage and serious pollution to the environment are caused due to the fact that most of antibiotics in China have the defects of low raw material utilization rate, low extraction purity, high content of residual antibiotics in the sewage and the like.
As the antibiotic production sewage belongs to the refractory organic sewage, the strong inhibition effect of the residual antibiotic on the microorganism can cause the sewage treatment process to be complex, the cost to be high and the teaching effect to be unstable. Therefore, in the treatment of antibiotic sewage, the physical treatment can be used as a pretreatment method of subsequent biochemical treatment to reduce suspended matters in the water and biological inhibiting substances in the sewage. At present, the physical treatment methods mainly include coagulation, sedimentation, air-float, adsorption, reverse osmosis and filtration.
The coagulation method is that after coagulant is added, the particles losing charges are stirred to contact with each other to form flocculant, so that the flocculant is convenient to precipitate or filter to achieve the purpose of separation. After coagulation treatment, the concentration of pollutants can be effectively reduced, and the biodegradability of sewage can be improved. The common coagulants in the sewage treatment of antibiotic pharmacy are as follows: polyferric sulfate, ferric trichloride, ferric salts, polyaluminum ferric sulfate, Polyacrylamide (PAM), and the like. Sedimentation is the process of separating or removing suspended particles of higher density than water by gravity sedimentation.
The air flotation uses highly dispersed micro-bubbles as carriers to adsorb pollutants in sewage, so that the apparent density of the bubbles is less than that of water, and the bubbles float upwards to realize the process of solid-liquid separation or liquid-liquid separation. Generally including an aerated air-float, a dissolved air-float, a chemical air-float and an electrolytic air-float. The Xinchang pharmaceutical factory adopts a CAF vortex cavity air flotation device to pretreat pharmaceutical sewage. With proper drug composition, the average removal rate of CODcr can reach about 25%.
The adsorption method is to use a porous solid to adsorb some pollutants in the sewage to recover or remove the pollutants, thereby purifying the sewage. Commonly used adsorbents include activated carbon, activated coal, humic acid and adsorbent resins. The method has the advantages of low investment, simple process, convenient operation and convenient treatment.
The reverse osmosis method is to separate concentrated solution from dilute solution with semi-permeable membrane, apply pressure over the osmotic pressure of the solution with pressure difference as driving force, change the natural osmosis direction, and permeate the water pressure in the concentrated solution to one side of the dilute solution. The purposes of sewage concentration and purification are achieved.
Aerobic treatment method for antibiotic sewage
The common aerobic biological treatment method in the pharmaceutical wastewater mainly comprises the following steps: common activated sludge process, pressurized biochemical process, deep well aeration process, biological contact oxidation process, biological fluidized bed process, sequencing batch activated sludge process, etc.
The activated sludge process is a mature method for treating antibiotic sewage at home and abroad at present. The strengthening of pretreatment and the improvement of aeration method lead the device to operate stably, and become common methods for pharmaceutical factories in industrially developed countries by the 70 s of 20 th century. However, the disadvantages of the conventional activated sludge process are: the sewage needs to be diluted in a large amount, the air bubbles are more during operation, the sludge expansion is easy to occur, the excess sludge amount is large, the removal rate is not high, and secondary or multistage treatment is required to be frequently adopted. Therefore, in recent years, improvement of aeration method and microorganism immobilization technique and improvement of sewage treatment efficiency have become important components of research and development of activated sludge process.
Compared with the traditional activated sludge method, the pressurization biochemical method improves the concentration of dissolved oxygen, provides sufficient oxygen, is favorable for accelerating biodegradation, and is favorable for improving the impact load resistance of organisms.
Deep well aeration is a high speed activated sludge system. Compared with the conventional activated sludge process, the deep well aeration process has the following advantages: the oxygen utilization rate is high and is 10 times of that of the conventional aeration; the sludge load is high and is 2.5-4 times of that of the conventional activated sludge method; small occupied area, less investment, low operation cost, high efficiency and high average value. The COD removal rate can reach more than 70 percent, the water resistance is strong, the organic load impact capacity is strong, and the sludge bulking problem is avoided. The heat preservation effect is good.
The biological contact oxidation has the characteristics of activated sludge and biological membranes, and the treatment capacity is large. It can treat organic sewage which is easy to cause sludge bulking. In the sewage treatment of pharmaceutical industry, the pharmaceutical sewage is treated directly by biological contact oxidation or by anaerobic digestion and acidification as pretreatment process. However, in the case of treating pharmaceutical wastewater by the contact oxidation method, if the intake concentration is high, a large amount of foam may occur in the tank, and precautions and countermeasures should be taken during the operation.
The biological fluidized bed combines the advantages of a common activated sludge method and a biological filter process, and has the advantages of high volume load, high reaction speed, small occupied area and the like.
The Sequencing Batch Reactor (SBR) has the advantages of uniform water quality, no sludge backflow, impact resistance, high sludge activity, simple structure, flexible operation, less occupied area, less investment, stable operation and the like. The removal rate of the substrate is higher than that of the common activated sludge method and the like. It is more suitable for sewage treatment with intermittent discharge and large water quantity and water quality fluctuation. However, the SBR process has the disadvantages of sludge sedimentation and long time for separating sludge from water. Treating high-concentration sewage.
However, since the antibiotic industrial wastewater is a high-concentration organic wastewater, many processes require dilution of raw water by many times during pretreatment, which leads to an increase in cost.
The photocatalysis technology is considered to be a low-energy-consumption treatment technology with a very promising application prospect at present, but the application range is narrow due to the limitations of low light quantum yield, requirement of ultraviolet light and the like of the existing catalyst.
The ozone oxidation method has obvious effect on degrading antibiotics, but the use of ozone causes certain pollution to the environment.
The tubular radical oxidation process was developed on the basis of the wet air oxidation process. The wet air oxidation method was developed by Zimmer to man in the united states in 1994, and is also called the WAO method. The treatment method of adding the catalyst in the WAO method is called a tubular free radical oxidation method, which is called a WACO method for short. The method is characterized in that under the conditions of high temperature (200-280 ℃) and high pressure (2-8 MPa), oxygen-enriched gas or oxygen is used as an oxidant, the catalytic action of a catalyst is utilized to accelerate the respiratory reaction between organic matters in the sewage and the oxidant, so that the organic matters in the sewage and poisons containing N, S and the like are oxidized into CO2、N2、SO2、H2O, achieving the purpose of purification. For various industrial organic sewage, COD and NH with high chemical oxygen content or containing compounds which can not be degraded by a biochemical method3The N removal rate reaches more than 99 percent, post-treatment is not needed, and the emission standard can be reached only through one-time treatment.
The catalyst is added into the traditional wet oxidation treatment system, and the activation energy of the reaction is reduced, so that the temperature and the pressure of the reaction are reduced under the condition of not reducing the treatment effect, the oxidative decomposition capacity is improved, the reaction time is shortened, the reaction efficiency is improved, the corrosion of equipment is reduced, and the cost is reduced; ) Has the advantages of high purification efficiency, no secondary pollution, simple flow, small occupied area and the like;
however, the tubular radical oxidation catalyst is selective, and the sewage contains a plurality of organic matters with different types and structures, so that the catalyst needs to be screened. Patent CN108579753A discloses an antibiotic sewer pipe type free radical oxidation catalyst, but the catalyst activity is low, the COD removal rate does not meet the industrial requirement, and the catalyst is easy to deactivate and far from the industrial application standard.
Disclosure of Invention
The invention aims to solve the problems thatThe defects of the prior art provide a method for treating industrial difficult-to-biochemically sewage based on a continuous free radical generator, which has high catalytic activity, can be effectively suitable for treating high-concentration antibiotic-containing difficult-to-biochemically sewage, and has CODcrThe removal rate is more than 90 percent, and BOD is obtained after treatment5/CODcr>0.3, the biodegradability of the sewage is increased, and the sewage can reach the standard after advanced treatment.
In order to realize the aim, the invention provides a method for treating industrial biochemical-difficult sewage based on a continuous free radical generator, which is characterized in that a tubular continuous reaction device is adopted in the method, the device comprises a fixed bed reactor, a high-pressure buffer tank, an air compressor, a condenser, a sewage tank, a sewage pump and a high-pressure separation tank, the air compressor is connected with an inlet of the high-pressure buffer tank, an outlet of the high-pressure buffer tank is connected with the fixed bed reactor, one end of the sewage pump is connected with the sewage tank, the other end of the sewage pump is connected with the fixed bed reactor, the condenser is arranged at an outlet of the fixed bed reactor, a condensation outlet is connected with the high-pressure separation tank, an exhaust hole is arranged at the top end of the high-pressure separation tank, and a collection hole is arranged at the bottom of the high-pressure separation tank; the fixed bed reactor is filled with a catalyst with the composition of MoO3-V2O5The Cu-CNTS comprises the following components in percentage by mass: 75-98.5% of carrier CNTS and 1.5-25% of active components, wherein the molar ratio of MoO3-V2O5/Cu-CNTS is 1: 0.1-10: 5 to 15.
When the device is used, the catalyst is loaded in the fixed bed reactor in advance, sewage to be treated in the sewage pool is pumped into the heat exchanger through the sewage pump to be subjected to heat exchange and then enters the fixed bed reactor, the sewage enters the high-pressure buffer tank through the air compressor to reach the preset pressure and then is led into the fixed bed reactor, the sewage to be treated and air from the high-pressure buffer tank in the fixed bed reactor are subjected to wet oxidation reaction under the action of the catalyst, macromolecular organic matters in the sewage in the fixed bed reactor are subjected to oxidative decomposition by the strong oxidant under certain pressure and temperature conditions, double bonds in the organic matter structure are broken and are oxidized into micromolecules by the macromolecules, the micromolecules are further oxidized into carbon dioxide and water, the COD is greatly reduced, the BOD/COD value is improved, the biodegradability of the sewage is increased, and the standard discharge can be achieved after the advanced treatment. Purified sewage flows into the heat exchanger through a water outlet of the fixed bed reactor and enters the high-pressure separation tank after being cooled, uncondensed gas is discharged through the exhaust holes, and liquid is collected through the collection port.
Preferably, the reaction temperature is 130-210 ℃, the reaction pressure is 2.2-3.5 MPa, and the liquid space velocity is 0.7-3.6 h-1And the flow rate of oxygen or air is 50-400 ml/min.
The preparation method of the catalyst comprises the following steps:
1) preparation of copper-doped carbon nanotubes:
mixing melamine and copper salt according to a ratio to obtain a mixture, then placing the mixture into a ball mill for ball milling for 5-6 hours, sieving the ball-milled mixture with a 200-mesh sieve, then drying the mixture for 1-3 hours in vacuum, and finally calcining the mixture for 5-10 hours at 800-1200 ℃ to obtain a copper-doped carbon nanotube;
2) dissolving a molybdenum precursor and ammonium metavanadate in ammonia water according to a certain molar ratio to obtain a mixed solution, then adding a certain amount of copper-doped carbon nano tube into the mixed solution, carrying out ultrasonic treatment at 10-40 ℃ for 1-10 hours, drying the slurry subjected to ultrasonic impregnation in vacuum for 5-24 hours, grinding the obtained sample, and roasting the ground sample in a muffle furnace at a high temperature for a period of time to obtain a powdery catalyst MoO3-V2O5/Cu-CNTS。
In the step 1), the copper salt is selected from one or more of copper chloride, copper nitrate, copper sulfate and copper bromide; the molar ratio of the copper salt to the melamine is 5-10: 1;
the molybdenum precursor in the step 2) is selected from one or more of molybdic acid, ammonium molybdate and dimolybdic acid; the molar ratio of the precursor of the molybdenum to the amine metavanadate is 1: 0.1-10; the concentration of the ammonia water is 0.5-0.8 mol/L, and the adding amount of the ammonia water is controlled to ensure that the molar concentration of the molybdenum in the mixed solution is 0.1-0.5 mol/L.
In the step 2), the temperature of vacuum drying is 80-120 ℃; the roasting temperature in a muffle furnace is 400-600 ℃, and the roasting time is 4-48 h.
The chemical property of the oxidation state molybdenum of the bamboo active metal molybdenum adopted by the invention is stable, because the molybdenum is very difficult to discard seven and eight electrons, the chemical property of the MoO3 with the highest valence state is determined to be stable, the molybdenum is stable in air or water at normal temperature or at a not too high temperature, and the molybdenum has a large amount of oxides with intermediate valence states except the highest valence state, such as high-activity oxides of MoO2, Mo4O11, Mo4O11, Mo17O47, Mo5O14, Mo8O23, Mo18O52, Mo9O26, Mo2O3 and MoO, so that the variable valence state of the MoO3 in a reaction system is very wide, and the catalytic capability of the antibiotic-containing sewage with complex composition is more excellent in biochemical treatment, but the catalytic capability of the antibiotic-containing sewage with complex composition is not ideal when the molybdenum is used alone due to the strong stability of the MoO 3. Vanadium, in turn, belongs to the moderately active metals, having valences +2, +3, +4 and + 5. Wherein, the valence state 5 is the most stable, and the valence state 4 is the second, the compound of the pentavalent vanadium has oxidation performance, and the low valence vanadium has reduction performance. The lower the valence state of vanadium is, the stronger the reducibility is, the addition of vanadium can generate a synergistic effect with MoO3 in the catalyst process, so that vanadium is converted into an intermediate valence state with higher catalytic activity, and the catalytic activity of the catalyst is greatly improved. The invention uses melamine as carbon source, automatically obtains the carbon nano tube which is doped with nitrogen atoms and has a six-membered ring with a stable structure in the calcining process, and then obtains the copper-modified carbon nano tube through the copper salt reaction, so that the obtained carbon nano tube has better binding capacity with the active component of the catalyst while the microstructure is stable, and the catalytic activity is further improved by using the carbon nano tube as a carrier catalyst.
Compared with the prior art, the invention has the beneficial effects that:
1) the process of the invention adopts air as the oxidant, the equipment occupies small area, the long-term operation cost is low, and the process is safe and controllable; convenient and practical, the catalyst reaction activity is high, and thorough to getting rid of the pollutant, do not produce poisonous and harmful gas among the sewage treatment process, do not produce mud, do not have secondary pollution.
2) The components of the composite catalyst have synergistic effect, the temperature and pressure required by oxidation reaction are reduced, the treatment effect is improved, the time for sewage retention treatment is reduced, the oxidation efficiency is improved, the investment and the production cost of a treatment device are reduced, the COD of the inlet sewage is 8000-100000mg/L, the outlet water can be directly discharged or subjected to biochemistry, the CODcr removal rate can reach more than 95% at most, and the treated BOD5/CODcr is more than 0.3.
Drawings
FIG. 1 shows a tubular continuous reaction apparatus according to the present invention
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
As shown in fig. 1, tubular free radical oxidation treatment device, including adopting tubular continuous reaction unit, the device includes fixed bed reactor 1, high-pressure buffer tank 2, air compressor machine 3, condenser 4, effluent water sump 5, sewage pump 6, high-pressure knockout drum 7, heat exchanger 8, air compressor machine 3 links to each other with high-pressure buffer tank 2's entry, high-pressure buffer tank 2 export links to each other with fixed bed reactor 1, 5 one end of sewage pump link to each other with the effluent water sump, the other end links to each other with heat exchanger 8, heat exchanger 8 export fixed bed reactor 1 links to each other, fixed bed reactor 1 exit set up condenser 4, the condensation export is connected with high- pressure knockout drum 6, 6 tops of high-pressure knockout drum are equipped with the exhaust hole, and the bottom is equipped with collects the mouth.
When the device is used, the catalyst is loaded in the fixed bed reactor 1 in advance, sewage to be treated in a sewage pool is pumped into the heat exchanger 8 through the sewage pump 5 to exchange heat and then enters the fixed bed reactor 1, the sewage enters the high-pressure buffer tank 2 through the air compressor to reach preset pressure and then is guided into the fixed bed reactor 1, wet oxidation reaction is carried out on the sewage to be treated and air from the high-pressure buffer tank 2 in the fixed bed reactor 1 under the action of the catalyst, macromolecular organic matters in the sewage in the fixed bed reactor 1 are oxidized and decomposed by the strong oxidant under certain pressure and temperature conditions, double bonds in the organic matter structure are broken and are oxidized into micromolecules by the macromolecules, and the micromolecules are further oxidized into carbon dioxide and water, so that the COD is greatly reduced, the BOD/COD value is improved, the biodegradability of the sewage is increased, and the standard discharge can be achieved. Purified sewage flows into a heat exchanger 8 through a water outlet of the fixed bed reactor 1 to be cooled and then enters a high-pressure separation tank 7, uncondensed gas is discharged from an exhaust hole, and liquid is collected by a collection port.
[ example 1 ]
1) Preparation of copper-doped carbon nanotubes:
mixing 100mol of melamine and 20mol of copper salt to obtain a mixture, then putting the mixture into a ball mill for ball milling for 6 hours, sieving the ball milled mixture with a 200-mesh sieve, then drying the mixture for 3 hours in vacuum, and finally calcining the mixture for 10 hours at 1200 ℃ to obtain a copper-doped carbon nanotube;
2) dissolving 1mol of molybdic acid and 1mol of ammonium metavanadate in 2L of ammonia water with the concentration of 0.8mol/L to obtain a mixed solution, then adding 600g of the copper-doped carbon nanotube prepared in the step 1 into the mixed solution, carrying out ultrasonic treatment at 20 ℃ for 2 hours, carrying out vacuum drying on the slurry subjected to ultrasonic impregnation at 100 ℃ for 10 hours, grinding the obtained sample, and then roasting in a muffle furnace at a high temperature for a period of time, wherein the roasting temperature is 600 ℃, and the roasting time is 24 hours to obtain the powdery catalyst MoO3-V2O 5/CNTS.
[ example 2 ]
1) Preparation of copper-doped carbon nanotubes:
mixing 100mol of melamine and 10mol of copper salt to obtain a mixture, then putting the mixture into a ball mill for ball milling for 6 hours, sieving the ball milled mixture with a 200-mesh sieve, then drying the mixture for 3 hours in vacuum, and finally calcining the mixture for 10 hours at 1200 ℃ to obtain a copper-doped carbon nanotube;
2) dissolving 1mol of molybdic acid and 0.5mol of ammonium metavanadate in 4L of ammonia water with the concentration of 0.8mol/L to obtain a mixed solution, then adding 600g of the copper-doped carbon nanotube prepared in the step 1 into the mixed solution, carrying out ultrasonic treatment at 20 ℃ for 2 hours, carrying out vacuum drying on the slurry subjected to ultrasonic impregnation at 100 ℃ for 10 hours, grinding the obtained sample, and roasting in a muffle furnace at a high temperature for a period of time, wherein the roasting temperature is 400 ℃, and the roasting time is 32 hours to obtain the powdery catalyst MoO3-V2O 5/CNTS.
Comparative example 1
1) Preparing the carbon nano tube:
putting melamine into a ball mill for ball milling for 5 hours, sieving the ball milled mixture through a 200-mesh sieve, then carrying out vacuum drying for 3 hours, and finally calcining for 10 hours at 1200 ℃ to obtain the carbon nano tube;
2) dissolving 1mol of molybdic acid and 5mol of ammonium metavanadate in 3L of ammonia water with the concentration of 0.8mol/L to obtain a mixed solution, then adding 500g of carbon nano tube into the mixed solution, carrying out ultrasonic treatment at 40 ℃ for 2 hours, carrying out vacuum drying on the slurry after ultrasonic impregnation at 80 ℃ for 10 hours, grinding the obtained sample, and then roasting in a muffle furnace at high temperature for a period of time, wherein the roasting temperature is 500 ℃, and the roasting time is 24 hours to obtain the powdery catalyst MoO3-V2O 5/CNTS.
Comparative example 2
1) Preparation of copper-doped carbon nanotubes:
mixing 100mol of melamine and 20mol of copper salt to obtain a mixture, then putting the mixture into a ball mill for ball milling for 6 hours, sieving the ball milled mixture with a 200-mesh sieve, then drying the mixture for 3 hours in vacuum, and finally calcining the mixture for 10 hours at 1200 ℃ to obtain a copper-doped carbon nanotube;
2) dissolving 1mol of ammonium molybdate in 3L of ammonia water with the concentration of 0.8mol/L to obtain a mixed solution, then adding 500g of the copper-doped carbon nano tube prepared in the step 1 into the mixed solution, carrying out ultrasonic treatment at 40 ℃ for 2 hours, carrying out vacuum drying on the slurry subjected to ultrasonic impregnation at 80 ℃ for 10 hours, grinding the obtained sample, and roasting in a muffle furnace at a high temperature for a period of time, wherein the roasting temperature is 500 ℃, and the roasting time is 24 hours to obtain the powdery catalyst MoO 3/Cu-CNTS.
Comparative example 3
1) Preparation of copper-doped carbon nanotubes:
mixing 100mol of melamine and 20mol of copper salt to obtain a mixture, then putting the mixture into a ball mill for ball milling for 6 hours, sieving the ball milled mixture with a 200-mesh sieve, then drying the mixture for 3 hours in vacuum, and finally calcining the mixture for 10 hours at 1200 ℃ to obtain the copper-doped carbon nanotube Cu-CNTS.
[ example 3 ]
And (3) treating sample sewage:
the sample sewage is mixed sewage of tetracycline and oxytetracycline, and the water quality detection indexes are as follows: CODcr is 10000-28000 mg/L, BOD5/CODcr is less than 0.3.
According to the apparatus shown in FIG. 1, the granular catalysts prepared in examples 1 to 2 and comparative examples 1 to 2 were loaded into the catalyst bed layer in the fixed bed reactor 1, the pressure of the air compressor 3 and the high pressure buffer tank 2 was adjusted to a set pressure, the fixed bed reactor was heated to a set temperature, air and sample sewage were fed together at a certain feed rate, and after 3 hours, COD test analysis was performed from the reaction solution, and the removal rate of COD was shown in Table 1.
TABLE 1
The foregoing description has disclosed fully preferred embodiments of the present invention. It should be noted that those skilled in the art can make modifications to the embodiments of the present invention without departing from the scope of the appended claims. Accordingly, the scope of the appended claims is not to be limited to the specific embodiments described above.
Claims (7)
1. A method for treating industrial difficult biochemical sewage based on a continuous free radical generator is characterized in that a tubular continuous reaction device is adopted in the method, the device comprises a fixed bed reactor, a high-pressure buffer tank, an air compressor, a condenser, a sewage pool, a sewage pump and a high-pressure separation tank, the air compressor is connected with an inlet of the high-pressure buffer tank, an outlet of the high-pressure buffer tank is connected with the fixed bed reactor, one end of the sewage pump is connected with the sewage pool, the other end of the sewage pump is connected with the fixed bed reactor, the condenser is arranged at an outlet of the fixed bed reactor, a condensation outlet is connected with the high-pressure separation tank, an exhaust hole is formed in the top end of the high-pressure separation tank, and a collection hole is formed in the bottom of the high-pressure separation tank; the fixed bed reactor is filled with a catalyst with the composition of MoO3-V2O5The Cu-CNTS comprises the following components in percentage by mass: 75 to 98.5 percent of CNTS as a carrier and 1.5 to 25 percent of active component, wherein MoO3-V2O5The mol ratio of Mo, V and Cu in the/Cu-CNTS is 1: 0.1-10: 5 to 15.
2. The method for treating industrial wastewater difficult to biochemically use based on the continuous free radical generator as claimed in claim 1, wherein in use, the catalyst is pre-loaded in the fixed bed reactor, the wastewater to be treated in the wastewater tank is pumped into the heat exchanger through the wastewater pump to exchange heat, then enters the fixed bed reactor, enters the high pressure buffer tank through the air compressor to reach a preset pressure, then is introduced into the fixed bed reactor, the wastewater to be treated in the fixed bed reactor and the air from the high pressure buffer tank undergo a wet oxidation reaction under the action of the catalyst, macromolecular organic matters in the wastewater in the fixed bed reactor are oxidized and decomposed by the strong oxidant under certain pressure and temperature conditions, double bonds in the organic matter structure are broken, and are oxidized into small molecules, and the small molecules are further oxidized into carbon dioxide and COD, so that BOD/value of COD is greatly reduced, the biochemical property of sewage is increased, the sewage can be discharged after advanced treatment, the purified sewage flows into the heat exchanger through the water outlet of the fixed bed reactor and then enters the high-pressure separation tank after being cooled, the uncondensed gas is discharged by the exhaust holes, and the liquid is collected by the collection port.
3. The method for treating industrial biochemical-difficult sewage based on the continuous free radical generator as claimed in claim 1, wherein the reaction temperature is 130-210 ℃, the reaction pressure is 2.2-3.5 MPa, the liquid space velocity is 0.7-3.6 h < -1 >, and the oxygen or air flow rate is 50-400 ml/min.
4. The method for treating industrial biochemical-difficult sewage based on the continuous free radical generator as claimed in claim 1, wherein the preparation method of the catalyst comprises the following steps:
1) preparation of copper-doped carbon nanotubes:
mixing melamine and copper salt according to a ratio to obtain a mixture, then placing the mixture into a ball mill for ball milling for 5-6 hours, sieving the ball-milled mixture with a 200-mesh sieve, then drying the mixture for 1-3 hours in vacuum, and finally calcining the mixture for 5-10 hours at 800-1200 ℃ to obtain a copper-doped carbon nanotube;
2) dissolving a molybdenum precursor and ammonium metavanadate in ammonia water according to a certain molar ratio to obtain a mixed solution, then adding a certain amount of copper-doped carbon nano tubes into the mixed solution, carrying out ultrasonic treatment at 10-40 ℃ for 1-10 hours, drying the ultrasonically-impregnated slurry in vacuum for 5-24 hours, grinding the obtained sample, and roasting the ground sample in a muffle furnace at a high temperature for a period of time to obtain the powdery catalyst MoO3-V2O 5/Cu-CNTS.
5. The method for treating industrial biochemical-difficult sewage based on the continuous free radical generator as claimed in claim 4, wherein in the step 1), the copper salt is selected from one or more of copper chloride, copper nitrate, copper sulfate and copper bromide; the molar ratio of the copper salt to the melamine is 5-10: 1.
6. The method for treating the industrial biochemical-difficult sewage based on the continuous free radical generator according to claim 4, wherein in the step 2), the molybdenum precursor is selected from one or more of molybdic acid, ammonium molybdate and dimolybdic acid; the molar ratio of the precursor of the molybdenum to the amine metavanadate is 1: 0.1-10.
7. The method for treating industrial biochemical-difficult sewage based on the continuous free radical generator according to claim 4, wherein in the step 2), the concentration of ammonia water is 0.5mol/L to 0.8mol/L, and the adding amount of ammonia water is controlled so that the molar concentration of molybdenum in the mixed solution is between 0.1mol/L to 0.5 mol/L; the temperature of vacuum drying is 80-120 ℃; the roasting temperature in a muffle furnace is 400-600 ℃, and the roasting time is 4-48 h.
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| CN101475285A (en) * | 2009-01-19 | 2009-07-08 | 辽宁天意实业股份有限公司 | Gas field sewerage and solid pollutant comprehensive processing technological process |
| CN101607203A (en) * | 2009-07-16 | 2009-12-23 | 浙江大学 | Be used to remove the Catalysts and its preparation method of dioxin-type halogenated aromatic compounds |
| CN101780411A (en) * | 2010-01-11 | 2010-07-21 | 华南师范大学 | CNT (carbon nano tube) loaded Pt-HxMoO3 catalyst, preparation method and application thereof |
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| CN101475285A (en) * | 2009-01-19 | 2009-07-08 | 辽宁天意实业股份有限公司 | Gas field sewerage and solid pollutant comprehensive processing technological process |
| CN101607203A (en) * | 2009-07-16 | 2009-12-23 | 浙江大学 | Be used to remove the Catalysts and its preparation method of dioxin-type halogenated aromatic compounds |
| CN101780411A (en) * | 2010-01-11 | 2010-07-21 | 华南师范大学 | CNT (carbon nano tube) loaded Pt-HxMoO3 catalyst, preparation method and application thereof |
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