CN105645557B - A kind of catalytic wet oxidation processing method of recirculated water - Google Patents
A kind of catalytic wet oxidation processing method of recirculated water Download PDFInfo
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- CN105645557B CN105645557B CN201410731310.0A CN201410731310A CN105645557B CN 105645557 B CN105645557 B CN 105645557B CN 201410731310 A CN201410731310 A CN 201410731310A CN 105645557 B CN105645557 B CN 105645557B
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Abstract
The invention discloses a kind of catalytic wet oxidation processing methods of recirculated water, extension recirculated water enters catalytic wet oxidation reactor from circulation, loads fixed bed catalyst in reactor, in normal conditions, control pressure is normal pressure, and temperature is 30~90 DEG C;When there is material leakage, control pressure is 0.1~2.5MPa, and temperature is 90~180 DEG C;The catalyst includes carrier and the active metal component being supported on carrier, wherein using transition metal and rare earth metal as active metal component, transition metal is the base metal in the 4th and 5 periods in the periodic table of elements, carrier is using the activated carbon of the mesh of 150 mesh~300 as core, using amorphous alumina as shell, wherein activated carbon accounts for the 30%~70% of vehicle weight, and aluminium oxide accounts for the 30%~70% of vehicle weight.The present invention can efficiently remove organic matter and S in recirculated water when nominal situation and circulating water quality fluctuate2‑, water outlet can be returned in circulation, ensure that the operation steady in a long-term of circulation.
Description
Technical field
The invention belongs to environmental protections and industrial energy saving water-saving technology field, and in particular to a kind of catalytic wet of recirculated water
Oxidation treatment method.
Background technology
The industrial circulating water system majority in China uses unenclosed construction, easy cooperating microorganisms;And in circulating water
In system, heat transmission equipment uses for a long time, can be because material leakage occur in the reasons such as corrosion, and organic materials can make recirculated water COD bright
Aobvious raising, these organic matters can provide nutrition for microorganism, the procreation of microorganism promoted to grow, biological clay is caused to endanger.
If contain organic acid, S in material2-Corrosive substances are waited, can also aggravate fouling and equipment corrosion.Therefore, in circulation
In, continuous supplementation is needed largely to supplement water(Generally select fresh surface water or underground water), a part is as circulating water
System evaporation loss, the supplement of air cooling tower windage loss water, another part, which is used as, to be ensured that circulating water quality is stable, avoids disliking because of water quality
Change and cold exchange device corrosion and scaling and rate of heat exchange is caused to decline and need to be supplemented by the water of circulation blowdown.This two
Part supplement water in, the magnitude of recruitment as circulation evaporation loss, air cooling tower windage loss water be usually it is constant, mainly
Depending on the temperature of environment and the form of air cooling tower;And second part stablizes needs by the circulatory system as guarantee circulating water quality
Blowdown water supplement then influenced by circulating water quality and on circulating water treatment technology, as in recirculated water suspended matter it is dense
Degree, bacterium and the content of microorganism, total solids content, the source for supplementing water and water quality arrange the processing that circulating water quality is taken
It applies.
Current circular water treating system mainly uses and various types of antisludging agents, corrosion inhibiter, sterilization is added into system
The chemical agents such as agent and the treatment measures such as by-passing filter oil removal are made to small part water, and focus mostly on to recirculated water
In the exploitation of the chemical agent of reason, such as various organic phosphates, energy and Ca2+、Mg2+Chelating agent Quadrafos of complexing etc..
CN1125697A discloses application and its application method of a kind of biological cleanser in circulation, relates generally to one kind and follows
Material leakage, biological clay, the new removal of bacterium algae and control method in ring water system;It is related to a kind of being compounded with biological agent
Have inhibition, scale inhibition decontamination, antibacterial multi-functional compound novel water quality stabilizer.CN200510025392.8 discloses one kind
The method that microorganism growth is controlled in circulation, adds in chlorination dodecyl dimethyl benzyl first in circulation
The mixture of base ammonium and isothiazolinone, then adds in Polyol Phosphate in circulation.Above-mentioned addition fungicide, table
The methods of face activating agent and biological enzyme formulation, dosing initial stage can in control loop water system microorganism growth, it is but micro-
Biology itself has certain tolerance and drug resistance, with the extension of time, the drug resistance enhancing of microorganism, then added
Pharmaceutical quantities can gradually increase, and expensive medicament certainly will increase operating cost, and medicament is become after failure as new pollutant.Together
When the biological clay killed release COD again, provide growth to the recirculated water microorganism that band is come in again in cyclic process
Required nutriment, so also having biological regrowth, it is impossible to fundamentally solve the growth of microorganism and breeding and life
Object foundry loam is led to the problem of.For the recirculated water of a certain specific water quality, suitable chemical agent is selected to be handled and really can
Play the role of stable circulating water quality, anti-corrosion, antiscale, kill microorganism, but during to circulating water treatment, due to the party
The characteristics of method, which determines, still will appear problems described above.
The present circulating water treatment device of construction is this to few in circulation mostly by the blowdown of other filter tank part
Part water does the measure of bypass processing, mainly using the filler filled in filter, for retaining suspended matter, mud in water removal
Sand, colloid and graininess impurity make turbidity in 10mg/L hereinafter, maintaining circulating water quality by being arranged outside the recirculated water of part simultaneously
Stablize.US6086772(EP0893412)A kind of method of pre- waterproof system recirculated water biological pollution is disclosed, in water cyclic system
Ozone generator is placed in system, the ozone of high concentration is generated by ozone generator, instead of fungicide such as chlorine etc., is completed to following
The bactericidal effect of aquatic organism and microbial contamination is recycled in ring water system, but this method is improved only in circulating water quality because of life
Object pollution caused by problem, in recirculated water because of organic acid, S2-Circulating water quality deteriorates caused by waiting corrosive substances etc.
Problem is not had an effect substantially.
In conclusion using due to water quality during chemical agent complexity, the diversity of chemical agent, between medicament and medicine
Undesirable chemical reaction can inevitably occur between agent and recirculated water, and chemical agent must periodically quantify addition, it is improper to grasp
It can accelerate the deterioration of water quality instead, generate opposite effect, while be become after the chemical agent failure added in as new pollution
Object, while the solid content in recirculated water cannot be reduced, the outer row's processing in part is still needed under normal circumstances.To few in circulation
Part water makees the measure of by-passing filter oil removal processing, and the suspended matter that can only also alleviate or partly solve in recirculated water is brought
Biological clay problem, it is impossible to effective utilizable substance of degrading microorganism.And reach certain treatment effect, need
Control low-down cycles of concentration.The two is used in combination, and partial bypass filters while chemical agent is added, but also only controls
Make low-down cycles of concentration(Such as less than 2.0), the normal operation of circulation could be effectively maintained, it is relatively low due to using
Cycles of concentration, system needs to discharge a large amount of sewage, while need to supplement a large amount of fresh waters into the circulatory system, this is not only caused
The waste of great lot of water resources increases quantity of wastewater effluent, and increases production cost.
Wet oxidation process(Wet air oxidation, WAO)Refer in certain temperature(180~320 DEG C)And certain pressure
(0.5~20MPa)Under, using the oxygen in air as oxidant, in liquid-phase system, the oxidation operation in waste water is decomposed into
The process of inorganic matter or small organic molecule.Due to being carried out under high temperature, condition of high voltage, required energy consumption is larger.Catalytic wet
Oxidation technology(Catalytic Wet Air Oxidation, CWAO)It is to add in urge in traditional wet oxidation system for handling
Agent reduces the activation energy of reaction, so as in the case where not reducing treatment effect, reduce the temperature and pressure of reaction, improves
The ability of oxygenolysis shortens the time of reaction, improves reaction efficiency.But develop at present the catalyst choice that uses and
Limited activity, and there is no low power consuming efficient reliable so far containing the organic matter that numerous species are different with structure in waste water
Catalyst.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of catalytic wet oxidation processing methods of recirculated water.This hair
It is bright that part recirculated water is drawn and is handled using catalytic wet air oxidation, it is fluctuated in nominal situation and circulating water quality
When, it can efficiently remove the organic matter and S in recirculated water2-, water outlet can be returned in circulation, ensure that circulating water
The operation steady in a long-term of system.
The catalytic wet oxidation processing method of recirculated water of the present invention includes following content:The extension from circulation
Recirculated water enters catalytic wet oxidation reactor, loads fixed bed catalyst bed in reactor, in normal conditions, control is urged
The pressure for changing wet oxidation is normal pressure, and temperature is 30~90 DEG C;When there is material leakage COD in recirculated water being caused to increase,
The pressure for controlling wet oxidation is 0.1~2.5MPa, and temperature is 90~180 DEG C;Processing Posterior circle water is discharged into gas-liquid separator, point
The purified gas separated out is used for preheated oxidant, is returned in circulation after purified water recovered heat;The catalyst packet
Carrier and the active metal component being supported on carrier are included, wherein using transition metal and rare earth metal as active metal component, mistake
Cross base metal of the metal for the 4th and 5 periods in the periodic table of elements, carrier be using the activated carbon of the mesh of 150 mesh~300 as core, with
Amorphous alumina is shell, and wherein activated carbon accounts for the 30%~70% of vehicle weight, and aluminium oxide accounts for the 30%~70% of vehicle weight.
In the present invention, 0.1%~10% is drawn from circulation, preferably draws 0.5%~3.0% recirculated water entrance
Catalytic wet oxidation reactor for treatment.
In the present invention, in normal conditions, the pollutant concentration in recirculated water is not high, therefore can control wet oxidation
Pressure is normal pressure, and temperature is 30~60 DEG C;When there is material leakage, when leading to the COD raisings in recirculated water, wet oxidation is controlled
Pressure for 0.3~2.0MPa, temperature is 100~160 DEG C;Residence time of the recirculated water in reactor is 0.1~3.0h, excellent
It is selected as 0.5~1.5 h.Concrete operations pressure and temperature needs are regulated and controled according to the raised degree of COD in recirculated water.
In the present invention, catalytic wet oxidation needs to be passed through air, oxygen or ozone as oxidant.In nominal situation
Under, it is preferable to use ozone for oxidant;When there is material leakage, when causing the COD in recirculated water to increase, oxidant using air or
Oxygen.When the temperature of catalytic wet oxidation is higher, the high temperature purification gas heated oxidant discharged by gas-liquid separator is to urging
Change the temperature needed for wet oxidation reaction, so as to further recycle heat, help to improve catalytic wet oxidation reaction effect.
In the present invention, in under-stream period, heater or high temperature material heat cycles water to be cooled may be used to required
Temperature;After pending system enters stationary phase, the high temperature purification water warm-up cycle water that gas-liquid separator separates go out may be used
To required temperature, if the temperature needed for catalytic wet oxidation cannot be reached after preheating, heater or height may be used
Temperature material to be cooled is heated to required temperature.Manifold pressure can make recirculated water that vapour not occur by booster pump pressurization control
Change.
Transition metal is one or more in vanadium, chromium, manganese, iron, cobalt, copper and titanium in catalyst of the present invention, mistake
The content for crossing metal oxide is 1%~15%;The rare earth metal is lanthanum, one or more in cerium, rare earth metal oxidation
The content of object is 1%~15%.
The preparation method of catalyst of the present invention is:During amorphous alumina plastic, 150 mesh~300 are introduced
Purpose activated carbon is beaten the slurries to be formed, and the material after obtained plastic carries out aging, is filtered, washed, dries, and catalyst is made
Carrier, impregnating metal component, is then dried on a catalyst support, is roasted under inert gas shielding, obtains catalytic wet oxygen
Change catalyst.
Activated carbon property used in the present invention is as follows:500~3000m of specific surface area2/ g, hole hold 0.5~1.8cm3/ g,
1~10nm of average pore radius.Activated carbon mashing using using plus water, one or more in low-carbon alcohols be beaten, wherein low
Carbon alcohol is one or more in the monohydric alcohol that carbon atom number is 1~5.
Activated carbon used in the present invention is preferably first handled using amino acid, is then beaten.The amino acid is
It is one or more in aspartic acid, glutamic acid, lysine.The amino acid dosage accounts for the 2% ~ 50% of activated carbon weight, preferably
It is 5% ~ 20%.Amino acid processing activated carbon can directly mix amino acid with activated carbon, can also amino acid be dissolved in solvent
In add activated carbon, solvent therein is water, low-carbon alcohols(I.e. carbon atom number is 1 ~ 5 monohydric alcohol)In it is one or more.
In the present invention, gas-liquid separation may be used pressure reducing mode and isolate gas in recirculated water, control gas-liquid separator
Interior pressure is 0.1~2.0MPa, reduces vapor loss as far as possible.The high temperature purification water of gas-liquid separator discharge can be with treating
The recirculated water of wet oxidation processing exchanges heat, and recycles heat, wet oxidation operation energy consumption is reduced, after temperature is down to less than 40 DEG C
It returns in circulation.
The method of the present invention is suitable for containing organic matter and S2-The processing of the recirculated water of pollutants is waited, can particularly there is effect
Fluctuation to cycle water system water quality ensures the operation steady in a long-term of cycle water system.
Compared with prior art, the method for the present invention has following prominent characteristics:
1st, the pollutant concentration in circulation is not high, but when heat transmission equipment leaks, it may appear that recirculated water
System Local C OD is very high, be easy to cause biological self reproducing, Stickydeposit and cause heat exchanger heat exchange efficiency decline, block and equipment
The problems such as corrosion.Although this high COD recirculated waters account for a seldom part for recirculated water system, work as this strand high COD recirculated waters
Still circulation and circulating water treatment system can be caused to impact into circulation, prior art means are mainly
A large amount of fresh waters are supplemented, are unfavorable for water-saving and emission-reducing.Present invention process process has by the operating condition of flexible modulation system for handling
Effect alleviates circulation leads to the decline of heat exchanger heat exchange efficiency, blocking and equipment corrosion due to biological self reproducing, Stickydeposit
The problems such as, operation is flexible, is increased without the chemical reagent of other organic or inorganics, will not generate secondary pollution.It is purified to follow
Ring coolant-temperature gage is very high, can be used for heating material to be heated, energy is fully used.
2nd, using the equally higher catalyst of catalytic wet oxidation activity under cryogenic, more conventional catalytic wet oxidation
Temperature and pressure needed for catalyst substantially reduces, and does not need to run at high temperature under high pressure for a long time, handles energy consumption and operation
Cost significantly reduces.
3rd, the heat of the high-temperature material in circulation, by circulating water heating to reaction temperature, the height after reaction are utilized
Warm purified water can be used for heating water inlet, and entire processing procedure does not have the loss of energy.The method of the present invention good economy performance, in not shadow
In the case of ringing normal production, while can be with efficient process recirculated water, do not need to increase additional energy, greatly reduce processing
Cost.
Description of the drawings
Fig. 1 is a kind of process flow chart of industrial circulation water treatment method of the present invention.
Specific embodiment
The extension recirculated water in circulation, recirculated water COD are often fluctuated, and COD exists under normal circumstances
50~200mg/L, when there is situations such as material is largely revealed, COD(Cr methods, similarly hereinafter)It can reach 1000~10000mg/L.
0.1%~10% is drawn from circulation, the recirculated water for preferably drawing 0.5%~3.0% enters catalytic wet oxidation reactor
It handles, fixed bed catalyst bed is filled in reactor, volume space velocity is 0.5~5h- 1.Under normal circumstances, recirculated water enters
Catalytic wet oxidation device is handled, and using ozone as oxidant, operating pressure is normal pressure, and temperature is 30~90 DEG C, can
To use high-temperature material by circulating water heating.When material leakage occurs, recirculated water COD significantly increases, then passes through high temperature substrate first
Circulating water heating to 90-180 DEG C, into catalytic wet oxidation reactor, is passed through oxygen or air as oxidant by material so that
Reactor pressure is 0.1~2.5MPa, catalytic wet oxidation reaction is carried out, by the organic matter and S in recirculated water2-Etc. being oxidized to
CO2、H2The substances such as O and sulfate, the water outlet after reaction are discharged into gas-liquid separator and carry out gas-liquid separation, the high temperature separated
Purified gas, by heat exchanger preheated oxidant, the high temperature purification water isolated is used for by heat exchanger after heating material to be heated,
It returns in circulation.
Commercially available powdery coconut husk charcoal specific surface area 928m used in the present invention2/ g, hole hold 1.0cm3/ g, average pore radius
1.1nm, iodine sorption value 700mg/g, 200 mesh of granularity.
The preparation method of catalyst used in the embodiment of the present invention is:910g Solid aluminum sulfates are added in distilled water,
It heats and stirs to dissolving simultaneously, obtain solution (a).Concentrated ammonia liquor is added in into appropriate distilled water and is diluted to about 10wt% weak aqua ammonias
(b).271g powderies coconut husk charcoal is added in glutamic acid (34g) aqueous solution and is uniformly mixed, it is 5 that liquid, which consolidates volume ratio,:1, then add water
Mashing, obtains activated carbon slurries (c).A plastic cans is taken, after (a) is added in tank and is heated with stirring to 60 DEG C, opens the appearance for having (b)
The valve of device controls and system in tank is added drop-wise to pH=4.0 within 10 minutes, opens the valve of (c) container, continues that (b) is added dropwise,
It controls in 30 minutes and system in tank is added drop-wise to pH=8.0, control the valve of the container of (c), guarantee is added dropwise to complete at this time.It keeps
Temperature is 60 DEG C, and material in tank is filtered by pH=8.0, aging 1 hour, is washed to sulfate radical-free ion, filtering, by filter cake
It is 10 hours dry at 110 DEG C, carrier material is obtained, is then roasted 5 hours under the conditions of 550 DEG C under nitrogen protection, is crushed
Sieving obtains powder carrier.100 grams of carrier material is taken, contacts to form paste with the peptization liquid containing nitric acid, extruded moulding,
Then it is 10 hours dry at 110 DEG C, after being roasted 5 hours under the conditions of 550 DEG C under nitrogen protection, with the maceration extract containing Ce-Cu
Dipping, it is then 10 hours dry at 110 DEG C, it is roasted 5 hours under the conditions of 550 DEG C under nitrogen protection, obtains catalyst A.It urges
CeO in agent2:9.63wt%, CuO:9.95wt%, specific surface area 433m2/ g, Kong Rong:0.37cm3/ g, side pressure strength:183N/
Cm, rate of wear:0.62wt%, granularity 1.5mm.
The above-mentioned preparation process of repetition, does not add amino acid during plastic, obtained catalyst B, CeO in catalyst2:
9.60wt%, CuO:9.90wt%, specific surface area:413 m2/ g, Kong Rong:0.35cm3/ g, side pressure strength:180N/cm, rate of wear:
0.82wt%, granularity 1.5mm.
Embodiment 1
The quantity of circulating water of certain circulation is 200 ton hours, and under nominal situation, COD is 80~100mg/L.From cycle
The recirculated water that 2.0%, temperature is 40~45 DEG C is drawn in water system and enters catalytic wet oxidation reactor for treatment, is passed through ozone work
For oxidant, pressure is normal pressure, and temperature is the temperature of recirculated water itself, and the residence time is 0.9 hour.Catalytic wet oxidation is reacted
The catalyst A, air speed 1.5h that in device prepared by filling the method for the present invention-1.After treatment, the COD of circulation can be dropped
To below 20mg/L.
When material leakage, this section of recirculated water COD is up to 300mg/L.In this case, lead to first with high-temperature material
Heat exchanger is crossed by the circulating water heating of extraction to 100 DEG C, is passed through oxygen as oxidant, control pressure 0.6-0.8MPa.Instead
Device water outlet is answered to enter gas-liquid separator, discharge gas is used for preheated oxidant, and high-temperature water heats material to be heated by heat exchanger, treats
Temperature is down to 40 DEG C hereinafter, returning in circulation.After processing in about 30 hours, the COD of recirculated water be down to 30mg/L with
Under.After water system to be recycled restores normal, stop high-temperature process, restore to temperature be 40-45 DEG C, normal pressure handles operating mode.
After the method for the present invention is handled, circulation COD stablizes in 20mg/L hereinafter, significantly slow after being used for a long time
Solved circulation causes the decline of heat exchanger heat exchange efficiency, equipment corrosion and blocking etc. to be asked due to biological self reproducing, Stickydeposit
Topic.
Embodiment 2
The quantity of circulating water of certain circulation is 200 ton hours, and under nominal situation, COD is 80~100mg/L.From cycle
The recirculated water that 2.0%, temperature is 40~45 DEG C is drawn in water system and enters catalytic wet oxidation reactor for treatment, is passed through ozone work
For oxidant, pressure is normal pressure, and temperature is the temperature of recirculated water itself, and the residence time is 0.9 hour.Catalytic wet oxidation is reacted
The catalyst B, air speed 1.5h that in device prepared by filling the method for the present invention-1.After long-term disposal, the COD of circulation begins
Eventually in below 25mg/L.
When material leakage, this section of recirculated water COD is up to 300mg/L.In this case, lead to first with high-temperature material
Heat exchanger is crossed by the circulating water heating of extraction to 110 DEG C, is passed through oxygen as oxidant, control pressure 0.8-1.0MPa.Instead
Device water outlet is answered to enter gas-liquid separator, discharge gas is used for preheated oxidant, and high-temperature water heats material to be heated by heat exchanger, treats
Temperature is down to 40 DEG C hereinafter, returning in circulation.After processing in about 35 hours, the COD of recirculated water be down to 30mg/L with
Under.After water system to be recycled restores normal, stop high-temperature process, restore to temperature be 40-45 DEG C, normal pressure handles operating mode.
After the method for the present invention is handled, circulation COD stablizes in 25mg/L hereinafter, significantly slow after being used for a long time
Solved circulation causes the decline of heat exchanger heat exchange efficiency, equipment corrosion and blocking etc. to be asked due to biological self reproducing, Stickydeposit
Topic.
Embodiment 3
The quantity of circulating water of certain circulation is 200 ton hours, and under nominal situation, COD is 60~120mg/L.From cycle
The recirculated water that 3.0%, temperature is 40~45 DEG C is drawn in water system and enters catalytic wet oxidation reactor for treatment, is passed through ozone work
For oxidant, pressure is normal pressure, and temperature is the temperature of recirculated water itself, and the residence time is 1.4 hours.Catalytic wet oxidation is reacted
The catalyst A, air speed 1.2h that in device prepared by filling the method for the present invention-1.After long-term disposal, the COD of circulation begins
Eventually in below 30mg/L.
When material leakage, this section of recirculated water COD is up to 1500mg/L.In this case, first with high-temperature material
By heat exchanger by the circulating water heating of extraction to 130 DEG C, oxygen is passed through as oxidant, control pressure 1.2-1.4MPa.
Reactor water outlet enters gas-liquid separator, and discharge gas is used for preheated oxidant, and high-temperature water heats material to be heated by heat exchanger,
Treat that temperature is down to 40 DEG C hereinafter, returning in circulation.After processing in about 40 hours, the COD of recirculated water is down to 40mg/L
Below.After water system to be recycled restores normal, stop high-temperature process, restore to temperature be 40-45 DEG C, normal pressure handles operating mode.
After the method for the present invention is handled, circulation COD stablizes in 30mg/L hereinafter, significantly slow after being used for a long time
Solved circulation causes the decline of heat exchanger heat exchange efficiency, equipment corrosion and blocking etc. to be asked due to biological self reproducing, Stickydeposit
Topic.
Embodiment 4
The quantity of circulating water of certain circulation is 200 ton hours, and under nominal situation, COD is 35~80mg/L.From cycle
The recirculated water that 2.5%, temperature is 40~45 DEG C is drawn in water system and enters catalytic wet oxidation reactor for treatment, is passed through ozone work
For oxidant, pressure is normal pressure, and temperature is the temperature of recirculated water itself, and the residence time is 1.3 hours.Catalytic wet oxidation is reacted
The catalyst B, air speed 1.1h that in device prepared by filling the method for the present invention-1.After long-term disposal, the COD of circulation begins
Eventually in below 30mg/L.
When material leakage, this section of recirculated water COD is up to 800mg/L.In this case, lead to first with high-temperature material
Heat exchanger is crossed by the circulating water heating of extraction to 120 DEG C, is passed through oxygen as oxidant, control pressure 1.1-1.2MPa.Instead
Device water outlet is answered to enter gas-liquid separator, discharge gas is used for preheated oxidant, and high-temperature water heats material to be heated by heat exchanger, treats
Temperature is down to 40 DEG C hereinafter, returning in circulation.After processing in about 45 hours, the COD of recirculated water be down to 40mg/L with
Under.After water system to be recycled restores normal, stop high-temperature process, restore to temperature be 40-45 DEG C, normal pressure handles operating mode.
After the method for the present invention is handled, circulation COD stablizes in 30mg/L hereinafter, significantly slow after being used for a long time
Solved circulation causes the decline of heat exchanger heat exchange efficiency, equipment corrosion and blocking etc. to be asked due to biological self reproducing, Stickydeposit
Topic.
Embodiment 5
Certain chemical plant circulation quantity of circulating water is 800 ton hours, circulating water cooling tower outlet COD for 55~
180mg/L.Wherein certain process units because material corrosion it is big, heat transmission equipment by for a long time use, there is corrosion failure, cause
Material is revealed.The process units quantity of circulating water is 15 ton hours, and recirculated water leaving water temperature is 40-45 DEG C, by monitoring recirculated water
Water outlet, COD is normally 100 ~ 200mg/L, and when there is material leakage, this section of recirculated water COD reaches as high as 7000mg/
L.It is handled using the method for the present invention, catalyst A, air speed 1h prepared by the built-in the method for the present invention of catalyst oxidation reactor-1。
Under normal circumstances, ozone is passed through as oxidant, and pressure is normal pressure, and temperature is the temperature of recirculated water itself, can recycle the section
Water COD is down to below 30mg/L.It, can be according to COD situations, to control the operating condition of wet oxidation, profit when there are COD raisings
With high-temperature material by heat exchanger by this section of circulating water heating to 160 DEG C, be passed through oxygen as oxidant, control pressure 1.6
~1.9MPa.Reactor water outlet enters gas-liquid separator, and discharge gas is used for preheated oxidant, and obtained high-temperature water enters heat exchanger
Heat material to be heated, after processing the COD of the device recirculated water be down to 40mg/L hereinafter, high-temperature water heated by heat exchanger it is to be added
Thermal material treats that temperature is down to 40 DEG C hereinafter, returning to circulation.After leakage investigation repairing, catalytic oxidation treatment device can be with
Restore to 40-45 DEG C, normal pressure to run.
After the method for the present invention is handled, the circulation circulating water cooling tower outlet COD stablize in 30mg/L hereinafter,
Alleviate circulation after long-time service significantly causes heat exchanger heat exchange efficiency to decline, set due to biological self reproducing, Stickydeposit
The problems such as standby corrosion and blocking.
Claims (13)
1. the catalytic wet oxidation processing method of a kind of recirculated water, it is characterised in that including following content:From circulation
Extension recirculated water enters catalytic wet oxidation reactor, fixed bed catalyst bed is loaded in reactor, in nominal situation
Under, the pressure for controlling catalytic wet oxidation is normal pressure, and temperature is 30~90 DEG C;Cause in recirculated water when there is material leakage
When COD is increased, the pressure for controlling catalytic wet oxidation is 0.1~2.5MPa, and temperature is 90~180 DEG C;After wet oxidation processing
Recirculated water be discharged into gas-liquid separator, the purified gas isolated is used for preheated oxidant, returns after purified water recovered heat and follows
In ring water system;The catalyst includes carrier and the active metal component that is supported on carrier, wherein with transition metal and
Rare earth metal is active metal component, and transition metal is the base metal in the 4th and 5 periods in the periodic table of elements, and rare earth metal is
It is one or more in lanthanum, cerium, carrier be using the activated carbon of the mesh of 150 mesh~300 as core, using amorphous alumina as shell, wherein
Activated carbon accounts for the 30%~70% of vehicle weight, and aluminium oxide accounts for the 30%~70% of vehicle weight;The preparation method of the catalyst is:
During amorphous alumina plastic, the activated carbon for introducing the mesh of 150 mesh~300 is beaten the slurries to be formed, after obtained plastic
Material carry out aging, be filtered, washed, dry, catalyst carrier is made, on a catalyst support impregnating metal component, then
It is dry, it is roasted under inert gas shielding, obtains catalytic wet oxidation catalyst;Wherein, activated carbon is first handled using amino acid,
Then it is beaten, amino acid processing activated carbon is directly to mix or amino acid is dissolved in solvent amino acid with activated carbon
In add activated carbon, it is one or more in the monohydric alcohol that solvent therein is water, carbon atom number is 1 ~ 5.
2. according to the method described in claim 1, it is characterized in that:0.1%~10% recirculated water is drawn from circulation
Into catalytic wet oxidation reactor for treatment.
3. according to the method described in claim 2, it is characterized in that:0.5%~3.0% recirculated water is drawn from circulation
Into catalytic wet oxidation reactor for treatment.
4. according to the method described in claim 1, it is characterized in that:In normal conditions, the pressure of catalytic wet oxidation is controlled
For normal pressure, temperature is 30~60 DEG C;When there is material leakage, control pressure is 0.3~2.0MPa, and temperature is 100~160
℃;Residence time of the recirculated water in reactor is 0.1~3.0h.
5. the method according to claim 1 or 4, it is characterised in that:Catalytic wet oxidation is passed through air, oxygen or ozone
As oxidant.
6. according to the method described in claim 5, it is characterized in that:In normal conditions, oxidant uses ozone;When there is object
During material leakage, oxidant uses air or oxygen.
7. according to the method described in claim 1, it is characterized in that:In under-stream period, using heater or high temperature object to be cooled
Expect heat cycles water to required temperature;After pending system enters stationary phase, the high temperature that is gone out using gas-liquid separator separates
Purified water warm-up cycle water if cannot reach the temperature needed for catalytic wet oxidation after preheating, then is adopted to required temperature
Required temperature is heated to heater or high temperature material to be cooled.
8. according to the method described in claim 1, it is characterized in that:In the catalyst transition metal be selected from vanadium, chromium, manganese, iron,
One or more in cobalt, copper and titanium, the content of transition metal oxide is 1%~15%;The content of rare-earth oxide is
1%~15%.
9. according to the method described in claim 1, it is characterized in that:The property of the activated carbon is as follows:Specific surface area 500~
3000m2/ g, hole hold 0.5~1.8cm3/ g, 1~10nm of average pore radius.
10. according to the method described in claim 1, it is characterized in that:Activated carbon mashing using plus water, one kind in low-carbon alcohols or
A variety of to be beaten, wherein low-carbon alcohols are one or more in the monohydric alcohol that carbon atom number is 1~5.
11. according to the method described in claim 1, it is characterized in that:The amino acid is aspartic acid, glutamic acid, relies ammonia
It is one or more in acid;Amino acid dosage accounts for the 2% ~ 50% of activated carbon weight.
12. according to the method for claim 11, it is characterised in that:The amino acid dosage account for activated carbon weight 5% ~
20%。
13. according to the method described in claim 1, it is characterized in that:Gas-liquid separation is isolated using pressure reducing mode in recirculated water
Gas, control gas-liquid separator in pressure be 0.1~2.0MPa;The purified water of gas-liquid separator discharge is with treating at wet oxidation
The recirculated water of reason exchanges heat, and temperature is returned after being down to less than 40 DEG C in circulation.
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CN109179791A (en) * | 2018-11-16 | 2019-01-11 | 佛山科学技术学院 | A kind of catalytic wet oxidation processing equipment of the industrial wastewater with multistage filtering |
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