CN110386655A - A method of based on the difficult biochemical sewage of continuous free-radical generator processing industry - Google Patents

A method of based on the difficult biochemical sewage of continuous free-radical generator processing industry Download PDF

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CN110386655A
CN110386655A CN201910693053.9A CN201910693053A CN110386655A CN 110386655 A CN110386655 A CN 110386655A CN 201910693053 A CN201910693053 A CN 201910693053A CN 110386655 A CN110386655 A CN 110386655A
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sewage
fixed bed
bed reactors
radical generator
processing industry
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CN110386655B (en
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周春松
贾建洪
孙坚
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Yixing International Environmental Protection City Technology Development Co Ltd
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Yixing International Environmental Protection City Technology Development Co Ltd
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    • 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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • 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
    • 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

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  • Chemical & Material Sciences (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)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

The present invention provides a kind of method based on the difficult biochemical sewage of continuous free-radical generator processing industry, uses air as oxidant, occupation area of equipment is small, and longtime running is at low cost, and process safety is controllable；It is convenient and practical, catalyst reaction activity is high, it is thorough to the removal of pollutant, toxic and harmful gas is not generated in sewage disposal process, does not generate sludge, without secondary pollution, water inlet COD of sewage 8000-100000mg/L, water outlet direct emission or can enter biochemical, and CODcr removal rate reaches as high as 95% or more, BOD5/CODcr > 0.3 after processing.

Description

A method of based on the difficult biochemical sewage of continuous free-radical generator processing industry
Technical field
It is the present invention relates to sewage treatment field, in particular to a kind of difficult biochemical based on the processing industry of continuous free-radical generator The method of sewage.
Background technique
Since China produces antibiotic since early 1950s, yield increases every year, has become and has led in the world One of antibiotics drug producing country wanted.In process of production, that there is raw material availabilities mostly is low, refines for China's antibiotic Purity is low, many deficiencies such as residual antibiotic content height in sewage, thus production waste complicated component, difficult etc. is caused to ask Topic, causes seriously to pollute to environment.
Since antibiotics production sewage belongs to difficult-degradation organic sewage, residual antibiotic acts on the strong inhibition of microorganism It will lead to that sewage disposal process is complicated, at high cost, teaching efficiency is unstable.Therefore, in the processing of antibiotic sewage, at physics Reason can be used as the preprocess method of subsequent biochemical processing, to reduce the suspended matter in water, reduce the biological inhibition substance in sewage. Currently, physical treatment method mainly has Coagulation Method, sedimentation, gas floatation process, absorption method, hyperfiltration and filtration method.
Coagulation Method is to contact with each other to form flocculant by the particle that stirring loses charge, just after coagulant is added In its precipitating or filter to achieve the purpose that separation.After coagulating treatment, it can be not only effectively reduced the concentration of pollutant, but also The biodegradability of sewage can be improved.There is common coagulant in the processing of antibiotic pharmacy sewage: bodied ferric sulfate, tri-chlorination Iron, molysite, polymeric ferric sulfate, polyacrylamide (PAM) etc..Precipitating is will suspension more higher than water density by gravity precipitating The process of particle separation or removal.
Air bearing is the pollutant using the microbubble of high degree of dispersion as carrier, in absorption effluent, keeps the apparent density of bubble small It in the apparent density of water, floats up, realizes the process of separation of solid and liquid or Liquid liquid Separation.Generally include inflation air bearing, solution gas Floating, chemical floatation and electrofloatation.Xinchang pharmaceutical factory pre-processes pharmacy sewage using CAF vortex cavity air-floating apparatus. Drug composition appropriate, the average removal rate of CODcr is up to 25% or so.
Absorption method, which refers to using certain pollutants in porosu solid absorption effluent, to be recycled or clears the pollution off, thus only Change sewage.Common adsorbent includes active carbon, active coal, humic acid and absorption resin.This method small investment, simple process, Easy to operate, processing is convenient.
Reverse osmosis is to be separated concentrated solution from weak solution using semi-permeable membrane, using pressure difference as driving force, is applied Add the pressure more than solution osmotic pressure, changes naturally osmotic direction, the hydraulic pressure in concentrate solution is penetrated into the side of weak solution. Sewage concentration, purification are achieved the purpose that.
Antibiotic sewage aerobic facture
Mainly there is common aerobic biological process for treating in pharmacy sewage: conventional activated sludge process, compression biochemical method, deep-well Aeration, biological contact oxidation process, organism fluidization bed process, sequencing batch active sludge etc..
Activated sludge process is the maturation method for handling antibiotic sewage both at home and abroad at present.Due to pretreated reinforcement, aeration The improvement of method keeps device stable, in the 1970s, having become commonly side, some pharmaceutical factories, industrially developed country Method.But the shortcomings that conventional activated sludge process is: sewage needs Macrodilution, and bubble is more in operation, Yi Fasheng sludge bulking, remains Remaining sludge quantity is big, and removal rate is not high, it is necessary to through frequently with second level or multistep treatment.Therefore, in recent years, aeration method and micro- is improved Biological fixation technology improves the important component that sewage treating efficiency has become activated sludge process research and development.
Compared with traditional activated sludge process, compression biochemical method improves dissolved oxygen concentration, provides sufficient oxygen, no Only be conducive to accelerate biodegrade, and be conducive to improve biological capacity of resisting impact load.
Deep well aeration is a kind of high rate activated sludge system.Compared with conventional activated sludge method, deep well aeration method have with Lower advantage: coefficient of oxygen utilization is high, is 10 times of conventional aeration；Sludge loading is high, is 2.5~4 times of conventional activated sludge method；Land occupation Area is small, and small investment, operating cost is low, high-efficient, and average value is high.For COD removal rate up to 70% or more, water resistance is strong, organic Load impact ability is strong, and sludge bulking problem is not present.Heat insulation effect is good.
The characteristics of active sludge of bio-contact oxidation and biomembrane, treating capacity is big.It, which can handle, is easy to cause dirt The organic sewage of mud expansion.In pharmaceuticals industry sewage treatment, bio-contact oxidation is often directly used, or be acidified with anaerobic digestion For pretreating process, treatment of pharmacy sewage.However, when using contact oxidation method treatment of pharmacy sewage, if inhaled concentration is high, It is possible that a large amount of foams, should take prevention and counter-measure in operation in pond.
Biological fluidized bed combines the advantages of conventional activated sludge process and biological filtering tank process, has volumetric loading high, anti- Answer the advantages that speed is fast, occupied area is small.
Sequencing batch active sludge (SBR) has water quality uniform, simple without sludge reflux, impact resistance, sludge activity height, structure List, flexible operation, land occupation less, small investment, it is stable the advantages that.The removal rate of matrix is higher than conventional activated sludge process etc..It More suitable for intermittent discharge, water and the big sewage treatment of variation water quality.But there are sludge settlings and sludge to be separated from water for SBR method The disadvantage of time length.In processing high-concentration sewage.
But since antibiotic trade effluent is high concentration organic sewage, so big Alternative need to be to original in preceding processing Water carries out more times of dilutions, so as to cause increased costs.
Photocatalysis technology is presently believed to be a kind of very promising low energy consumption processing technique, but due to existing rank Limitation, the application ranges such as its quantum yield of the catalyst of section is low, needs ultraviolet light conditions are also relatively narrow.
Ozonation is more obvious to antibiotic degradation effect, but will also result in certain dirt to environment using ozone Dye.
Tubular type free-radical oxidation method is grown up on the basis of wet air oxidation.Wet air oxidation is beauty Zimmer~man of state is in exploitation in 1994, also known as WAO method.The processing method that catalyst is added in WAO method is then referred to as Tubular type free-radical oxidation method, abbreviation WACO method.It refers under high temperature (200~280 DEG C), high pressure (2~8MPa), with oxygen rich air Body or oxygen are oxidant, using the catalytic action of catalyst, accelerate the respiratory reaction between dirty Organic substance in water and oxidant, make Organic matter in sewage and CO is oxidized to containing poisonous substances such as N, S2、N2、SO2、H2O reaches the purpose of purification.To high chemical oxygen content Or the various industrial organic sewages for the compound that cannot be degraded containing biochemical method, COD and NH3~N removal rate reaches 99% or more, no It is post-processed again, only through single treatment i.e. up to discharge standard.
Catalyst is added in traditional wet oxidation system for handling, reduces the activation energy of reaction, thus not reducing place In the case where managing effect, the temperature and pressure of reaction is reduced, the ability of oxygenolysis is improved, shortens the time of reaction, improved anti- Efficiency is answered, and reduces the corrosion of equipment and reduces costs；) have purification efficiency is high, without secondary pollution, process simply, account for The advantages that ground area is small；
But tubular type free-radical oxidation catalyst is selective, and different with structure containing numerous species organic in sewage Object needs to screen catalyst.A kind of antibiotic sewage tubular type free-radical oxidation is disclosed in patent CN108579753A Catalyst, but catalyst activity is lower, and industrial requirements are not achieved in COD removal rate and catalyst easy in inactivation is much not achieved industry and answers Use standard.
Summary of the invention
It is a kind of difficult based on the processing industry of continuous free-radical generator object of the present invention is in view of the deficiencies of the prior art, provide The method of biochemical sewage has catalytic activity high, can be effectively applicable to the processing of the high concentration biochemical sewage of difficulty containing antibiotic, CODcr Removal rate BOD after 90% or more, processing5/CODcr> 0.3, the biodegradability of sewage is increased, it can be up to standard after advanced treating Discharge.
In order to achieve the above-mentioned object of the invention, it is difficult raw based on the processing industry of continuous free-radical generator that the present invention provides one kind Change the method for sewage, it is characterised in that this method uses tubular type continuous reaction apparatus, and described device includes fixed bed reactors, height Press surge tank, air compressor machine, condenser, cesspool, sewage pump and high pressure knockout drum, the entrance of the air compressor machine and high-pressure buffering pot It is connected, the high-pressure buffering pot outlet is connected with fixed bed reactors, and described sewage pump one end is connected with cesspool, the other end It is connected with fixed bed reactors, condenser, condensate outlet and high pressure knockout drum phase is arranged in the fixed bed reactors exit Connection, the high pressure separation upper end are equipped with gas vent, and bottom is equipped with collection port；It is mounted in and urges in the fixed bed reactors Agent, group become MoO3-V2O5/ Cu-CNTS, the mass percentage of each component are as follows: support C NTS is 75%~98.5%, living Property group is divided into 1.5%~25%, wherein MoO3-V2O5/Cu-CNTS molar ratio be the molar ratio of Mo, V, Cu be 1:0.1~ 10:5~15.
In use, catalyst is pre-loaded in fixed bed reactors, by sewage pump by the dirt to be processed in cesspool Water, which is pumped into heat exchanger, enters fixed bed reactors after heat exchange, entered in high-pressure buffering pot by air compressor and reach default pressure It is imported in fixed bed reactors after power, treatment sewage is being catalyzed with the air from high-pressure buffering pot in fixed bed reactors Wet oxidation reaction occurs under the action of agent, big point under the conditions of certain pressure and temperature in fixed bed reactors in sewage Sub- organic matter is by strong oxidizer oxygenolysis, and double bond fracture in organic constitution is oxidized to small molecule, small molecule by macromolecular It is further oxidized to carbon dioxide and water, COD sharp fall BOD/COD value is improved, increases the biodegradability of sewage, is passed through It can qualified discharge after advanced treating.The sewage of purification is by entering high pressure after the cooling of fixed bed reactors water outlet inflow heat exchanger Knockout drum, uncooled gas point are vented by gas vent, and liquid is collected by collection port.
Preferably, 130~210 DEG C, 2.2~3.5MPa of reaction pressure of the reaction temperature, liquid air speed 0.7~ 3.6h-1, 50~400ml/min of oxygen or air velocity.
The method for preparing catalyst includes the following steps:
1) preparation of the carbon nanotube of Copper-cladding Aluminum Bar:
Melamine and mantoquita are proportionally carried out to be mixed to get mixture, then by mixture be put into ball mill into Row ball milling 5~6 hours, the mixture after ball milling is crossed into 200 meshes, is then dried in vacuo 1~3 hour, finally 800~1200 It is calcined 5~10 hours at DEG C, obtains the carbon nanotube of Copper-cladding Aluminum Bar；
2) presoma of molybdenum and ammonium metavanadate are dissolved in ammonium hydroxide by certain molar ratio and obtain mixed solution, then one The carbon nanotube of quantitative Copper-cladding Aluminum Bar is added in mixed solution, is ultrasonically treated 1~10 hour at 10~40 DEG C, and ultrasound is soaked Slurries after stain dry 5 under vacuum~for 24 hours, obtained sample is polished to roast a period of time in Muffle furnace high temperature, i.e., Obtain powder catalyst MoO3-V2O5/Cu-CNTS。
In step 1), the mantoquita is one or more in copper chloride, copper nitrate, copper sulphate, copper bromide；Mantoquita with The molar ratio of melamine is 5~10:1；
Molybdenum presoma described in step 2) is selected from one of molybdic acid, ammonium molybdate, two molybdic acids or a variety of；The presoma of molybdenum Molar ratio with metavanadic acid amine is 1:0.1~10；The concentration of ammonium hydroxide is 0.5mol/L~0.8mol/L, controls the addition of ammonium hydroxide Amount is so that the molar concentration of molybdenum is between 0.1mol/L~0.5mol/L in mixed solution.
In step 2), vacuum drying temperature is 80~120 DEG C；Maturing temperature in Muffle furnace is 400~600 DEG C, Calcining time is 4~48h.
The chemical property of the oxidation state molybdenum for the bamboo active metal molybdenum that the present invention uses is more stable, because molybdenum will lose seven or eight A electronics is very difficult, which dictates that the chemical property of the MoO3 of highest valence state is more stable, room temperature or less high At a temperature of, molybdenum is stable in air or water, and molybdenum is other than highest valence state, but there is the oxide of a large amount of intermediate valence states, Such as MoO2, Mo4O11, Mo4O11, Mo17O47, Mo5O14, Mo8O23, Mo18O52, Mo9O26 and Mo2O3 and the contour work of MoO Property oxide, this allows for MoO3, and variable valence is very extensive in the reaction system, thus in face of the high COD of complicated composition containing anti- The raw difficult biochemical sewage of element has more outstanding catalytic capability, but since the stronger stability of MoO3 makes it when being used alone Catalytic performance it is unsatisfactory.And vanadium belongs to medium active metal, chemical valence+2 ,+3 ,+4 and+5.It is wherein most with 5 valence states Stablize, followed by 4 valence states, the compound of pentavalent vanadium has oxidation susceptibility, and Low Valent Vanadium then has reproducibility.The valence state of vanadium is lower also Originality is stronger, and the addition of vanadium can generate synergistic effect in catalyst process and MoO3, and being allowed to be changed into, there is higher catalysis to live The intermediate valence state of property, substantially increases the catalytic activity of catalyst.The present invention is carbon source using melamine, in calcination process The carbon nanotube for automatically deriving doping nitrogen-atoms and the hexatomic ring with rock-steady structure is then that mantoquita reacts to obtain copper modification Carbon nanotube, make obtain carbon nanotube microstructure stablize while, have preferably combined with catalyst activity component Ability utilizes it as carried catalyst catalytic activity and further increases.
Compared with prior art, beneficial effects of the present invention:
1) technique of the invention uses air as oxidant, and occupation area of equipment is small, and longtime running is at low cost, process peace It is complete controllable；Convenient and practical, catalyst reaction activity is high, thorough to the removal of pollutant, does not generate in sewage disposal process toxic Pernicious gas does not generate sludge, without secondary pollution.
2) between composite catalyst each component of the invention have synergistic effect, temperature needed for reducing oxidation reaction and Pressure simultaneously improves treatment effect, and improving oxidation efficiency while reducing the time of sewage stop processing reduces processing dress The investment set and production cost, COD of sewage 8000-100000mg/L of intaking, water outlet direct emission or can enter biochemical, CODcr Removal rate reaches as high as 95% or more, BOD5/CODcr > 0.3 after processing.
Detailed description of the invention
Fig. 1 is tubular type continuous reaction apparatus of the present invention
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects It encloses.
As shown in Figure 1, tubular type free-radical oxidation processing unit, including use tubular type continuous reaction apparatus, described device packet Include fixed bed reactors 1, high-pressure buffering pot 2, air compressor machine 3, condenser 4, cesspool 5, sewage pump 6, high pressure knockout drum 7, heat exchange Device 8, the air compressor machine 3 are connected with the entrance of high-pressure buffering pot 2, the outlet of high-pressure buffering pot 2 and 1 phase of fixed bed reactors Even, described 5 one end of sewage pump is connected with cesspool, and the other end is connected with heat exchanger 8, and heat exchanger 8 exports fixed bed reactors 1 It is connected, condenser 4 is arranged in 1 exit of fixed bed reactors, and condensate outlet is connected with high pressure knockout drum 6, the height 6 top of knockout drum is pressed to be equipped with gas vent, bottom is equipped with collection port.
In use, catalyst is pre-loaded in fixed bed reactors 1, it will be to be processed in cesspool by sewage pump 5 Sewage, which is pumped into heat exchanger 8, enters fixed bed reactors 1 after heat exchange, entered in high-pressure buffering pot 2 by air compressor and reached After preset pressure import fixed bed reactors 1 in, in fixed bed reactors 1 treatment sewage with from high-pressure buffering pot 2 Wet oxidation reaction occurs under the effect of the catalyst for air, under the conditions of certain pressure and temperature in fixed bed reactors 1 Larger molecular organics in sewage are by strong oxidizer oxygenolysis, and double bond fracture in organic constitution is oxidized to by macromolecular Small molecule, small molecule are further oxidized to carbon dioxide and water, improve COD sharp fall BOD/COD value, increase sewage Biodegradability, can qualified discharge after advanced treating.The sewage of purification passes through 1 water outlet inflow heat exchanger of fixed bed reactors Enter high pressure knockout drum 7 after 8 coolings, uncooled gas point is vented by gas vent, and liquid is collected by collection port.
[embodiment 1]
1) preparation of the carbon nanotube of Copper-cladding Aluminum Bar:
It carries out 100mol melamine and 20mol mantoquita to be mixed to get mixture, mixture is then put into ball mill Interior progress ball milling 6 hours, crosses 200 meshes for the mixture after ball milling, is then dried in vacuo 3 hours, finally forges at 1200 DEG C It burns 10 hours, obtains the carbon nanotube of Copper-cladding Aluminum Bar；
2) 1mol molybdic acid and 1mol ammonium metavanadate are dissolved in 2L concentration is to obtain mixed solution in 0.8mol/L ammonium hydroxide, then Copper-cladding Aluminum Bar carbon nanotube prepared by the step 1 of 600g is added in mixed solution, is ultrasonically treated 2 hours, will surpass at 20 DEG C Slurries after sound dipping are dried in vacuo 10h at 100 DEG C, and obtained sample is polished when Muffle furnace high temperature roasts one section Between, 600 DEG C of maturing temperature, calcining time is for 24 hours up to powder catalyst MoO3-V2O5/CNTS.
[embodiment 2]
1) preparation of the carbon nanotube of Copper-cladding Aluminum Bar:
It carries out 100mol melamine and 10mol mantoquita to be mixed to get mixture, mixture is then put into ball mill Interior progress ball milling 6 hours, crosses 200 meshes for the mixture after ball milling, is then dried in vacuo 3 hours, finally forges at 1200 DEG C It burns 10 hours, obtains the carbon nanotube of Copper-cladding Aluminum Bar；
2) 1mol molybdic acid and 0.5mol ammonium metavanadate are dissolved in 4L concentration is to obtain mixed solution in 0.8mol/L ammonium hydroxide, so The Copper-cladding Aluminum Bar carbon nanotube afterwards prepared by the step 1 of 600g is added in mixed solution, is ultrasonically treated 2 hours at 20 DEG C, will Slurries after ultrasonic immersing are dried in vacuo 10h at 100 DEG C, and obtained sample is polished to roast one section in Muffle furnace high temperature Time, 400 DEG C of maturing temperature, calcining time is 32h up to powder catalyst MoO3-V2O5/CNTS.
[comparative example 1]
1) preparation of carbon nanotube:
Melamine is put into ball mill and is carried out ball milling 5 hours, the mixture after ball milling is crossed into 200 meshes, then very Sky is 3 hours dry, finally calcines 10 hours at 1200 DEG C, obtains carbon nanotube；
2) 1mol molybdic acid and 5mol ammonium metavanadate are dissolved in 3L concentration is to obtain mixed solution in 0.8mol/L ammonium hydroxide, then The carbon nanotube of 500g is added in mixed solution, is ultrasonically treated 2 hours at 40 DEG C, by the slurries after ultrasonic immersing in 80 10h is dried in vacuo at DEG C, obtained sample is polished to roast a period of time in Muffle furnace high temperature, 500 DEG C of maturing temperature, roasts Burning the time is for 24 hours up to powder catalyst MoO3-V2O5/CNTS.
[comparative example 2]
1) preparation of the carbon nanotube of Copper-cladding Aluminum Bar:
It carries out 100mol melamine and 20mol mantoquita to be mixed to get mixture, mixture is then put into ball mill Interior progress ball milling 6 hours, crosses 200 meshes for the mixture after ball milling, is then dried in vacuo 3 hours, finally forges at 1200 DEG C It burns 10 hours, obtains the carbon nanotube of Copper-cladding Aluminum Bar；
2) by 1mol ammonium molybdate be dissolved in 3L concentration be 0.8mol/L ammonium hydroxide in obtain mixed solution, then 500g the step of The Copper-cladding Aluminum Bar carbon nanotube of 1 preparation is added in mixed solution, is ultrasonically treated 2 hours at 40 DEG C, by the slurry after ultrasonic immersing Liquid is dried in vacuo 10h at 80 DEG C, and obtained sample is polished to roast a period of time, maturing temperature in Muffle furnace high temperature 500 DEG C, calcining time is for 24 hours up to powder catalyst MoO3/Cu-CNTS.
[comparative example 3]
1) preparation of the carbon nanotube of Copper-cladding Aluminum Bar:
It carries out 100mol melamine and 20mol mantoquita to be mixed to get mixture, mixture is then put into ball mill Interior progress ball milling 6 hours, crosses 200 meshes for the mixture after ball milling, is then dried in vacuo 3 hours, finally forges at 1200 DEG C It burns 10 hours, obtains the carbon nanotube Cu-CNTS of Copper-cladding Aluminum Bar.
[embodiment 3]
The processing of sample sewage:
Sample sewage be tetracycline and terramycin combined sewage, water quality detection index are as follows: CODcr be 10000~ 28000mg/L, BOD5/CODcr < 0.3.
Device as shown in Figure 1, it is anti-that the beaded catalyst that embodiment 1-2 and comparative example 1-2 are prepared is packed into fixed bed It answers in the catalyst bed in device 1, the pressure for adjusting air compressor machine 3 and high-pressure buffering pot 2 reaches setting pressure, and heating is fixed It rises to set temperature to bed reactor, and air and sample sewage are fed together with certain charging rate, from reaction after 3 hours Liquid, carries out COD test analysis, and the removal rate of COD is shown in Table 1.
Table 1
Above description sufficiently discloses a specific embodiment of the invention.It should be pointed out that being familiar with the field Range of any change that technical staff does a specific embodiment of the invention all without departing from claims of the present invention. Correspondingly, the scope of the claims of the invention is also not limited only to previous embodiment.

Claims (7)

1. a kind of method based on the difficult biochemical sewage of continuous free-radical generator processing industry, which is characterized in that this method uses Tubular type continuous reaction apparatus, described device include fixed bed reactors, high-pressure buffering pot, air compressor machine, condenser, cesspool, dirt Water pump and high pressure knockout drum, the air compressor machine are connected with the entrance of high-pressure buffering pot, the high-pressure buffering pot outlet and fixed bed Reactor is connected, and described sewage pump one end is connected with cesspool, and the other end is connected with fixed bed reactors, the fixed bed Condenser is arranged in reactor exit, and condensate outlet is connected with high pressure knockout drum, and the high pressure separation upper end is equipped with exhaust Hole, bottom are equipped with collection port；Mounted in there is catalyst in the fixed bed reactors, group becomes MoO3-V2O5/ Cu-CNTS, respectively The mass percentage of component are as follows: support C NTS is 75%~98.5%, and active component is 1.5%~25%, wherein MoO3- V2O5/Cu-CNTS molar ratio is that the molar ratio of Mo, V, Cu are 1:0.1~10:5~15.
2. the method according to claim 1 based on the difficult biochemical sewage of continuous free-radical generator processing industry, feature It is, in use, catalyst is pre-loaded in fixed bed reactors, is pumped the treatment sewage in cesspool by sewage pump Enter and enter fixed bed reactors after exchanging heat in heat exchanger, is entered in high-pressure buffering pot after reaching preset pressure by air compressor It imports in fixed bed reactors, treatment sewage and the air from high-pressure buffering pot are in catalyst in fixed bed reactors Effect is lower to occur wet oxidation reaction, and macromolecular under the conditions of certain pressure and temperature in fixed bed reactors in sewage has Machine object is by strong oxidizer oxygenolysis, double bond fracture in organic constitution, is oxidized to small molecule by macromolecular, and small molecule is into one Step is oxidized to carbon dioxide and water, improves COD sharp fall BOD/COD value, the biodegradability of sewage is increased, through depth After processing can qualified discharge, the sewage of purification by fixed bed reactors water outlet inflow heat exchanger it is cooling after enter high pressure and separate Tank, uncooled gas point are vented by gas vent, and liquid is collected by collection port.
3. the method according to claim 1 based on the difficult biochemical sewage of continuous free-radical generator processing industry, feature Be, 130~210 DEG C, 2.2~3.5MPa of reaction pressure of the reaction temperature, liquid 0.7~3.6h-1 of air speed, oxygen or 50~400ml/min of air velocity.
4. the method according to claim 1 based on the difficult biochemical sewage of continuous free-radical generator processing industry, feature It is, the method for preparing catalyst includes the following steps:
1) preparation of the carbon nanotube of Copper-cladding Aluminum Bar:
Melamine and mantoquita are proportionally carried out to be mixed to get mixture, then mixture is put into ball mill and carries out ball Mill 5~6 hours, crosses 200 meshes for the mixture after ball milling, is then dried in vacuo 1~3 hour, finally at 800~1200 DEG C Calcining 5~10 hours, obtains the carbon nanotube of Copper-cladding Aluminum Bar；
2) presoma of molybdenum and ammonium metavanadate are dissolved in ammonium hydroxide by certain molar ratio and obtain mixed solution, then a certain amount of Copper-cladding Aluminum Bar carbon nanotube be added mixed solution in, be ultrasonically treated 1~10 hour at 10~40 DEG C, after ultrasonic immersing Slurries dry 5 under vacuum~for 24 hours, obtained sample it is polished in Muffle furnace high temperature roasting a period of time to get powder Last shape catalyst MoO3-V2O5/Cu-CNTS.
5. the method according to claim 4 based on the difficult biochemical sewage of continuous free-radical generator processing industry, feature It is, in step 1), mantoquita is one or more in copper chloride, copper nitrate, copper sulphate, copper bromide；Mantoquita and melamine Molar ratio be 5~10:1.
6. the method according to claim 4 based on the difficult biochemical sewage of continuous free-radical generator processing industry, feature It is, in step 2), molybdenum presoma is selected from one of molybdic acid, ammonium molybdate, two molybdic acids or a variety of；The presoma of molybdenum and inclined vanadium The molar ratio of acid amide is 1:0.1~10.
7. the method according to claim 4 based on the difficult biochemical sewage of continuous free-radical generator processing industry, feature It is in step 2), the concentration of ammonium hydroxide is 0.5mol/L~0.8mol/L, and the additional amount for controlling ammonium hydroxide makes molybdenum in mixed solution Molar concentration between 0.1mol/L~0.5mol/L；Vacuum drying temperature is 80~120 DEG C；Roasting in Muffle furnace Temperature is 400~600 DEG C, and calcining time is 4~48h.
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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
US20100207053A1 (en) * 2009-02-13 2010-08-19 Sang-Hyo Ryu Catalyst composition for the synthesis of thin multi-walled carbon nanotube and its manufacturing method

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US20100207053A1 (en) * 2009-02-13 2010-08-19 Sang-Hyo Ryu Catalyst composition for the synthesis of thin multi-walled carbon nanotube and its manufacturing method
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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