CN1781606A - Method for treating waste water and method for regenerating catalyst detergent - Google Patents
Method for treating waste water and method for regenerating catalyst detergent Download PDFInfo
- Publication number
- CN1781606A CN1781606A CN 200510118578 CN200510118578A CN1781606A CN 1781606 A CN1781606 A CN 1781606A CN 200510118578 CN200510118578 CN 200510118578 CN 200510118578 A CN200510118578 A CN 200510118578A CN 1781606 A CN1781606 A CN 1781606A
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- Prior art keywords
- catalyst
- cleaning solution
- waste water
- water
- temperature
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- 239000003054 catalyst Substances 0.000 title claims abstract description 202
- 239000002351 wastewater Substances 0.000 title claims abstract description 186
- 238000000034 method Methods 0.000 title claims abstract description 88
- 239000003599 detergent Substances 0.000 title claims description 5
- 230000001172 regenerating effect Effects 0.000 title description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 103
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 93
- 239000001301 oxygen Substances 0.000 claims abstract description 92
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000007789 gas Substances 0.000 claims abstract description 53
- 239000007791 liquid phase Substances 0.000 claims abstract description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims description 108
- 239000007864 aqueous solution Substances 0.000 claims description 70
- 238000009279 wet oxidation reaction Methods 0.000 claims description 69
- 238000005406 washing Methods 0.000 claims description 66
- 239000000203 mixture Substances 0.000 claims description 63
- 230000000694 effects Effects 0.000 claims description 61
- 239000000243 solution Substances 0.000 claims description 56
- 238000004140 cleaning Methods 0.000 claims description 55
- 239000000126 substance Substances 0.000 claims description 52
- 238000011069 regeneration method Methods 0.000 claims description 41
- 238000004065 wastewater treatment Methods 0.000 claims description 41
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- 239000002184 metal Substances 0.000 claims description 36
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 23
- -1 nitrogen-containing compound Chemical class 0.000 claims description 23
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- 150000002739 metals Chemical class 0.000 claims description 19
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- 239000011777 magnesium Substances 0.000 claims description 17
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 16
- 229910052741 iridium Inorganic materials 0.000 claims description 16
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 16
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- 239000010941 cobalt Substances 0.000 claims description 15
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- Treatment Of Water By Oxidation Or Reduction (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to waste water treating process. The waste water treating process includes the following two steps: 1. wet oxidizing waste water containing at least one kind of nitride, organic matter and inorganic matter while maintaining at over 100 deg C and pressure on at least one part of waste water, in the presence of supported catalyst and in the presence of oxygen in the amount essential for decomposing nitride, organic matter and/or inorganic matter into nitrogen and/or CO2 and water; and 2. mixing at least one part of the high temperature liquid phase obtained through liquid-gas separating after wet oxidizing and waste water before treatment.
Description
The application is dividing an application of the Chinese patent application 00100415.8 submitted on January 31st, 2000.
The present invention relates to contain the processing method of the waste water (following abbreviate it as waste water) of at least a nitrogen-containing compound, organic substance and inorganic substances.
In addition, the washing regeneration method of catalyst system therefor during the wet oxidation that the invention still further relates to waste water is handled.According to catalyst washing regeneration method of the present invention, can wash the metal ingredient of removing attached on the heat exchanger in the waste water wet oxidation equipment, gas-liquid separation device, cooler, the various pipe arrangement classes etc. simultaneously.
The wet oxidation processing method that contains the waste water of at least a nitrogen-containing compound, organic substance and inorganic substances (below be generically and collectively referred to as " dirty composition ") is known.
Disclose a kind of in special public clear 59-29317 number that for example the applicant applies for by the processing of wet oxidation under supported catalyst existence condition waste water, the method for decomposing ammonia, organic substance and inorganic substances in the waste water.
As presentation of results shown in the embodiment, this method generally can be brought into play best water treatment effect.But, for this method, when dirty constituent concentration is high in waste water (for example the TOD value is that 65000mg/l is when above), owing to use relatively large air (oxygen) and under high temperature, condition of high voltage, handle, large quantity of moisture evaporation in heat exchanger, heater and reaction tower and transfer to gas phase.Therefore, reduce in order to handle the temperature that evaporation latent heat causes, must increase the heat exchanger heat transfer area or with externally heating such as external heaters, be difficult to keep good liquid phase state simultaneously and continue reaction, the clearance rate of dirty composition reduces.In addition, when the dirty constituent concentration in the waste water is high or the metal ingredient in the waste water when making its active reduction, can not well handle attached to catalyst surface.
And, relate to the prior art of wet oxidation processing method, for example open clear 54-42851 number, spy and open clear 55-152591 number, spy and open clear 62-132589 number, spy and open flat 3-777691 number, spy and open flat 4-104898 number for the spy opens clear 53-20663 number, spy.
In the wet oxidation method of these waste water, normally spherical to be carried on, granular, cylindric, fragment shape, cellular etc. has the state of carriers such as metal oxide carrier, the composite metal oxide carrier that contains at least a these metal oxides, absorbent charcoal carrier such as the silica, aluminium oxide, titanium oxide, zirconia of different shape, uses at least a in the water-insoluble of chosen from Fe, cobalt, nickel, magnesium, ruthenium, rhodium, palladium, iridium, platinum, copper, gold and tungsten and these metals and even the slightly water-soluble compound.Because this supported catalyst (being designated hereinafter simply as the wastewater oxidation catalyst) needs a large amount of the use when handling waste water, must make process cause active catalyst regeneration, the repeated use that reduces with the time of processing.The inventor finds that in advance the wastewater oxidation catalyst being carried out for two steps handles, promptly carry out pickling processes and carry out that liquid-phase reduction is handled or vapour phase reduction when handling with alkaline aqueous solution with acidic aqueous solution, activity of such catalysts is significantly recovered (with reference to special fair 3-66018 communique, below this method being called " application method formerly ").
This formerly application method can produce good catalyst regeneration effect, but owing to must carry out pickling processes and reduction and handled for two steps and handle, aspect practical, expectation adopts easier processing operation to reach same good effect.
Therefore, main purpose of the present invention is to provide a kind of new technology, when adopting this technology that the waste water that contains at least a nitrogen-containing compound, organic substance and inorganic substances is carried out wet oxidation, even use relatively large air (oxygen), the occasion of under high temperature, condition of high voltage, handling, do not need to increase externally heating such as heat exchanger heat transfer area or employing heater yet, and can keep good liquid phase state, continue reaction.
In addition, thus the present invention also aims to provide a kind of by suppressing metal ingredient attached to can be effectively on the catalyst surface and handle the new technology of the high waste water of dirty constituent concentration economically.
And main purpose of the present invention also is to provide a kind of novel wastewater treatment catalyst renovation process that can bring into play height catalyst regeneration effect by the convenient disposal operation.
Fig. 1 is the flow chart of expression one embodiment of the present invention.
Fig. 2 is the flow chart of expression another embodiment of the present invention.
The invention provides following method of wastewater treatment and catalyst washing regeneration method,
1. method of wastewater treatment (hereinafter referred to as " the 1st processing method ") is characterized in that comprising following two steps:
(1) pressure that keeps temperature more than 100 ℃ and at least a portion waste water to keep liquid phase, under the condition that supported catalyst exists, and the nitrogen-containing compound in the waste water and/or organic substance and/or inorganic substances be decomposed under the above oxygen existence condition of the necessary theoretical oxygen amount of nitrogen and/or carbon dioxide and water, the waste water that contains at least a nitrogen-containing compound, organic substance and inorganic substances is handled in wet oxidation;
(2) at least a portion of wet oxidation being handled the high-temperature liquid-phase that the back gas-liquid separation obtains circulates with waste water before wet oxidation is handled and mixes.
2. as 1 described method of wastewater treatment, the catalyst activity composition in the step (1) is at least a in the water-insoluble of chosen from Fe, cobalt, nickel, magnesium, ruthenium, rhodium, palladium, iridium, platinum, copper, gold and tungsten and these metals and even the insoluble chemical compound.
3. as 1 described method of wastewater treatment, liquidus speed (tower is gone into liquid measure/tower cross-sectional area) is 0.1～1.0cm/sec in the tower in the step (1).
4. as 1 described method of wastewater treatment, the oxygen source in the step (1) is air, rich oxygen containing air, high purity oxygen, ozone and H
2O
2In at least a.
5. as 1 described method of wastewater treatment, the internal circulating load of the high-temperature liquid-phase in the step (2) is 0.1～15 times of waste water.
6. method of wastewater treatment (hereinafter referred to as " second processing method ") is characterized in that comprising following five steps:
(1) pressure that keeps temperature more than 100 ℃ and at least a portion waste water to keep liquid phase, under the condition that supported catalyst exists, and the nitrogen-containing compound in the waste water and/or organic substance and/or inorganic substances be decomposed under the above gas that contains high purity oxygen (oxygen concentration is more than the 80%) existence condition of the necessary theoretical oxygen amount of nitrogen and/or carbon dioxide and water, the waste water that contains at least a nitrogen-containing compound, organic substance and inorganic substances is handled in wet oxidation
(2) at least a portion of wet oxidation being handled the high-temperature liquid-phase that back gas-liquid separation for the first time obtains circulates with waste water before wet oxidation is handled and mixes,
(3) carry out heat exchange between the waste water before the first time, High Temperature Gas liquid phase that gas-liquid separation obtains and wet oxidation were handled after, this gas-liquid is cooled off mutually, carry out the gas-liquid separation second time,
(4) liquid phase that gas-liquid separation is for the second time obtained is carried out biological processes, and
(5) excess sludge that produces in the biological processes is mixed with above-mentioned waste water circulation.
7. as 6 described method of wastewater treatment, contain in step (1) that oxygen concentration is more than 80% in the gas of high purity oxygen.
8. as 6 described method of wastewater treatment, the catalyst activity composition in the step (1) is at least a in the water-insoluble of chosen from Fe, cobalt, nickel, magnesium, ruthenium, rhodium, palladium, iridium, platinum, copper, gold and tungsten and these metals and even the insoluble chemical compound.
9. as 6 described method of wastewater treatment, liquidus speed (tower is gone into liquid measure/tower cross-sectional area) is 0.1～1.0cm/sec in the tower in the step (1).
10. as 6 described method of wastewater treatment, the oxygen source in the step (1) is rich oxygen containing air, high purity oxygen, ozone and H
2O
2In at least a.
11. as 6 described method of wastewater treatment, the internal circulating load of the middle high-temperature liquid-phase of step (2) is 0.1～15 times of waste water.
12. as 6 described method of wastewater treatment, the biological processes method in the step (4) is activated sludge process and/or biology denitrogenation.
13. catalyst washing regeneration method, it is characterized in that comprising the steps: to use acidic aqueous solution as cleaning solution with the supported catalyst washing regeneration method with the water-insoluble of iron, cobalt, nickel, magnesium, ruthenium, rhodium, palladium, iridium, platinum, copper, gold and tungsten and these metals and even at least a waste water wet oxidation in the insoluble chemical compound as the catalyst activity composition, and for cleaning solution 1m
3/ hr is with 10Nm
3The ratio bubbling air that/hr is above makes catalyst contact with cleaning solution under the temperature more than the normal temperature.
14. catalyst washing regeneration method, it is characterized in that comprising the steps: to use alkaline aqueous solution as cleaning solution with the supported catalyst washing regeneration method with the water-insoluble of iron, cobalt, nickel, magnesium, ruthenium, rhodium, palladium, iridium, platinum, copper, gold and tungsten and these metals and even at least a waste water wet oxidation in the insoluble chemical compound as the catalyst activity composition, and for cleaning solution 1m
3/ hr is with 10Nm
3The ratio bubbling air that/hr is above makes catalyst contact with cleaning solution under the temperature more than the normal temperature.
15. catalyst washing regeneration method, it is characterized in that comprising the steps: (1) use acidic aqueous solution as cleaning solution with the supported catalyst washing regeneration method with the water-insoluble of iron, cobalt, nickel, magnesium, ruthenium, rhodium, palladium, iridium, platinum, copper, gold and tungsten and these metals and even at least a waste water wet oxidation in the insoluble chemical compound as the catalyst activity composition, and for cleaning solution 1m
3/ hr is with 10Nm
3The ratio bubbling air that/hr is above makes catalyst contact with cleaning solution under the temperature more than the normal temperature; (2) use alkaline aqueous solution as cleaning solution, and for cleaning solution 1m
3/ hr is with 10Nm
3The ratio bubbling air that/hr is above makes catalyst contact with cleaning solution under the temperature more than the normal temperature.
16. catalyst washing regeneration method, it is characterized in that comprising the steps: (1) use alkaline aqueous solution as cleaning solution with the supported catalyst washing regeneration method with the water-insoluble of iron, cobalt, nickel, magnesium, ruthenium, rhodium, palladium, iridium, platinum, copper, gold and tungsten and these metals and even at least a waste water wet oxidation in the insoluble chemical compound as the catalyst activity composition, and for cleaning solution 1m
3/ hr is with 10Nm
3The ratio bubbling air that/hr is above makes catalyst contact with cleaning solution under the temperature more than the normal temperature; (2) use acidic aqueous solution as cleaning solution, and for cleaning solution 1m
3/ hr is with 10Nm
3The ratio bubbling air that/hr is above makes catalyst contact with cleaning solution under the temperature more than the normal temperature.
17. the catalyst detergent waste liquid and the waste water that produce at least a method in 13～16 are together carried out the catalyst washing regeneration method that wet oxidation is handled.
18. as 17 described catalyst washing regeneration methods, catalyst detergent liquid is carried out coagulation sedimentation handles, remove the metal ingredient in the liquid after, together carry out wet oxidation with waste water and handle.
I. relate to the invention of method of wastewater treatment
Handle the waste water of object as the present invention, as long as contain at least a nitrogen-containing compound, organic substance and inorganic substances, there is no particular limitation.
As the nitrogen-containing compound that contains in the waste water, for example be NH
4-N (be meant the nitrogen of ammonium form, below identical), NO
2-N, NO
3-N, organic nitrogen (comprising amine), inorganic nitrogen (comprising CN class, SCN class) etc.
As the organic substance that contains in the waste water, for example be generally organic substance (phenols, alcohols, carboxylic acids etc.), organochlorine compound (trichloro-ethylene, tetrachloro-ethylene, bioxin etc.), outstanding absurd creature matter (deriving from the mud that produces in organic class solid waste, the various biological processes step, garbage, municipal refuse, living beings class etc.).
The inorganic substances that contain in the waste water for example are generally inorganic substances (as S
2O
3 2-, SO
3 2-, SCN
-, CN
-Deng).
In addition, handle the waste water of object, for example contain the waste water of a kind of above-mentioned nitrogen-containing compound, organic substance and inorganic substances separately and contain the waste water of two or more these materials simultaneously as the present invention.
This waste water is for example handled the coke-fired furnace device for coal, coal gasification apparatus, the coal gas liquid that lique faction of coal device etc. produce, the waste water of in these devices, following coal gas to generate and producing, the waste water that wet type desulfurizing tower and wet type decyanation tower produce, photographic wastewater, printing wastewater, agricultural chemicals waste water, dyeing waste-water, semiconductor manufacturing factory waste water, petrochemical plant's waste water, the petroleum refinement plant chimney stalk, pharmaceutical factory's waste water, waste water of paper mill, chemical plant wastewater, contain garbage, paper, the sanitary wastewater of plastics etc., follow stool and urine, the waste water that the thermal decomposition of municipal refuse produces, follow biological treatment (the anaerobic processing of industrial wastewater, the aerobic processing) mud that produces, downflow sludge, follow the waste water of the oiling generation of downflow sludge, the waste water that contains organochlorine compound, the various cyanide bearing waste solutions that the plating industry is discharged, being used for nitriding steel with elimination handles, liquid soaks carbon to be handled, surface-treated cyanogen liquid such as chemical conversion processing, the cyanogen waste liquid of discharging in these surface treatment process etc.For example, above-mentioned cyanide wastewater also contains organochlorine compounds such as various organic and various nitrogen-containing compounds such as inorganic substances (organic acids such as formic acid, acetate etc.), ammonia (if following not special needs comprise that all nitrogen-containing compounds of cyanogen, ammonia are referred to as " nitrogen-containing compound "), trichloro-ethylene etc. sometimes simultaneously.
The present invention also is useful for the waste water that contains one or more metal ingredients such as Mg, Al, Si, P, Ca, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd or the processing of mud.
Following with reference to accompanying drawing, detailed explanation the present invention.
Fig. 1 is the flow chart of the embodiment of expression the 1st processing method.
Fig. 2 is the flow chart of the embodiment of expression the 2nd processing method.
In the 1st processing method, waste water is boosted to the pressure of regulation from former water pot by pump, mix the oxygen-containing gas that boosts with compressor again, use heat exchanger (abbreviating " heat is handed over " among Fig. 1 as) to be heated to the temperature of regulation then after, the supply response tower.
In the 2nd processing method, waste water is boosted to the pressure of regulation from former water pot by pump, mix the gas that contains high purity oxygen that boosts with compressor again, use heat exchanger (abbreviating " heat is handed over " among Fig. 2 as) to be heated to the temperature of regulation then after, the supply response tower.
Be filled with the catalyst of suppressed by vector load in the reaction tower.
The catalyst activity composition for example is the water-insoluble and even the insoluble chemical compound of iron, cobalt, nickel, magnesium, ruthenium, rhodium, palladium, iridium, platinum, copper, gold and tungsten and these metals.In particular, this compound for example is oxide (cobalt oxide, iron oxide etc.), chloride (ruthenous chloride, platinous chloride etc.), sulfide (sulfuration ruthenium, rhodium sulphide etc.) etc.These metals and compound thereof can use separately, also can be two or more use simultaneously, or with mixes the formation composite catalyst as ternary metal (for example La, Ce, Te etc.).These catalyst activity compositions can use with the state that is carried on known metal oxide carrier and the metallic carrier according to conventional method.
There is no particular limitation for metal oxide carrier and metallic carrier, can use the material that uses as the well-known catalysts carrier.Metal oxide carrier for example for aluminium oxide, silica, zirconia, titanium oxide, contain the composite metal oxide (alumina silica, alumina silica-zirconia, oxidation titania-zirconia etc.) of these metal oxides, be the metal oxide carrier etc. of main component with these metal oxides or composite metal oxide, metallic carrier for example is iron, aluminium etc.In these carriers, the more preferably zirconia that durability is good, titanium oxide and oxidation titania-zirconia.
Also there is no particular limitation to the shape of supported catalyst, for example spherical, graininess, cylindric, fragment shape, Powdered, cellular etc.When filling this supported catalyst, the reaction tower volume preferably can make the space velocity of liquid reach 0.5～10hr under the occasion of fixed bed
-1, more preferably reach 1～5hr
-1At supported catalyst is spherical, graininess, cylindric, fragment shape, Powdered etc. occasion, and the size of the supported catalyst that uses on the fixed bed is generally 3～50mm, more preferably 5～25mm.In addition, when catalyst cupport was used on honeycomb support, honeycomb structured body can use the material of peristome for arbitrary shapes such as quadrangle, hexagon, circles.There is no particular limitation to the area of per unit volume, aperture opening ratio etc., is 200～800m but use the area of per unit volume usually
2/ m
3, aperture opening ratio is 40～80% material.Material as honeycomb structured body for example is metal oxide and a metal same as described above, more preferably the zirconia that durability is good, titanium oxide and oxidation titania-zirconia.
The catalyst activity composition is generally 0.05～25 weight % with respect to the load capacity of carrier, more preferably 0.3～3 weight %.
In heat exchanger, recuperation of heat is carried out in the High Temperature Gas liquid phase circulation that following gas-liquid separator is obtained.In addition, wait in the winter time in the time of maybe must being elevated to set point of temperature in the time of can not keeping the regulation reaction temperature when reacting etc., also can adopt the heating of heater (not shown), or by steam generator (not shown) supply response tower steam.In addition, when going into operation,, also can directly steam be fed in the reaction tower and heat up, or the heater (not shown) is set between heat exchanger and reaction tower heats up in order to make the temperature in the reaction tower reach set point of temperature.
Temperature in the reaction tower is more than 100 ℃, more preferably more than 150 ℃.Temperature is high more during reaction, the decomposition clearance rate of dirty composition is high more, the waste water holdup time in the reaction tower also shortens in addition, owing to increase installation cost, preferably takes all factors into consideration decision reaction temperatures such as the dirty constituent concentration in the waste water, the degree that requires processing, running cost, cost of erection but then.
Pressure during reaction is preferably processed waste water and can keeps more than the pressure of liquid phase under reaction temperature.Here, " pressure that can keep liquid phase " is meant that oxygen concentration is under the condition of the gas feeding amount that contains high concentration oxygen more than 80% in the embodiment of oxygen-containing gas feeding amount, Fig. 2 in the reaction temperature of regulation and the embodiment of Fig. 1, in reaching the liquid of balance (waste water) amount, steam vapour amount and gas flow (gas flow in the tower except that steam), steam vapour amount is (more preferably below 50%) below 60%, can keep the pressure of liquid phase in the reaction tower in fact.
In addition, in the 2nd processing method, carry out biological processes because the back is handled in wet oxidation to handling water, reaction pressure significantly increases, and does not need to carry out the oxidation processes of hypervelocity.Can handle the kind of the waste water of object, the changes such as concentration of dirty composition according to conduct, for example can be at 10～20kg/cm
2Lower pressure under carry out wet oxidation and handle.
In the 1st kind of processing method, the oxygen amount of supply response tower is that nitrogen-containing compound, organic substance and inorganic substances are when being decomposed into harmless product more than the necessary theoretical oxygen amount, be more preferably 1～3 times of theoretical oxygen amount, 1.05～1.2 times of special preferably theoretical oxygen amount.Can use the material (O that can produce oxygen under air, rich oxygen containing air (the rich oxygen containing air that rich oxygen containing air, air-oxygen mixture, the employing PSA device processing air that uses the penetrating film of selectivity oxygen to obtain obtains etc.), oxygen and the wastewater treatment condition as oxygen source
3, H
2O
2Deng).
In the twoth kind of processing method, the oxygen amount of supply response tower is that nitrogen-containing compound, organic substance and inorganic substances are when being decomposed into harmless product more than the necessary theoretical oxygen amount, be more preferably 1.05～3 times of theoretical oxygen amount, 1.1～1.2 times of special preferably theoretical oxygen amount.Can use oxygen concentration as oxygen source is the high gas of oxygen concentration more than 80%, can produce the material (O of high concentration oxygen under for example rich oxygen containing air (use rich oxygen containing air, air-oxygen mixture that the penetrating film of selectivity oxygen obtains, adopt the PSA device to handle rich oxygen containing air that air obtains etc.), high purity oxygen and the wastewater treatment condition
3, H
2O
2Deng).
The 1st and the 2nd kind of processing method in, as oxygen source also can use contain one or more impurity contain oxygen waste gas, these impurity are hydrogen cyanide, hydrogen sulfide, ammonia, sulfur oxide, nitrogen oxide, hydrocarbon etc. for example.According to the present invention, the impurity in these oxygen sources also can together be decomposed with the processed composition in the waste water.
" theoretical oxygen amount " is meant that nitrogen-containing compound, organic substance and inorganic substances (processed composition) in the waste water are decomposed into harmless product (N in addition, in the present invention
2, H
2O and CO
2) time necessary oxygen amount.Can calculate it and decompose necessary oxygen amount by analyzing, be easy to obtain theoretical oxygen amount as the processed composition in the waste water of handling object.Aspect practical, can be based on experience and test, using Several Parameters to find out can the approximate relational expression that calculates theoretical oxygen amount of high accuracy.This relational expression for example is recorded in the special public clear 58-27999 communique.
The treatment fluid that is obtained by reaction tower is gas phase and liquid phase by first gas-liquid separator separates.The gas phase that obtains after the separation and the part of liquid phase are transported in the cooler after using as the waste water heating source in the heat exchanger as mentioned above, are transported in second gas-liquid separator again, are separated into gas phase (discharge gas) and liquid phase (processing water).
In the present invention, at least a portion that makes the HTHP liquid phase that is obtained by the 1st gas-liquid separator is circulated back to reaction tower (this cycling is called " heat recirculation ") through liquid circulating pipe road and circulating pump and mixes with waste water.The internal circulating load of liquid can be generally 0.1～15 times of wastewater flow rate, more preferably 1～10 times according to suitably decisions such as the activity of such catalysts reduction degree of filling in the proterties (kind of processed composition and concentration thereof etc.) of waste water, the reactor.Owing to formed fixed bed in the reaction tower, also carry out the washing of catalyst simultaneously, liquidus speed is generally 0.1～1.0cm/sec in the tower, more preferably 0.2～0.9cm/sec.
Liquid and gas beyond the above-mentioned circulating fluid, are separated in second gas-liquid separator and discharge gas and handle water after over-heat-exchanger is cooled the device cooling by the 1st gas-liquid separator.
The processing water that is obtained by the 2nd gas-liquid separator can also adopt conventional method to carry out biological processes (activated sludge process, biology denitrogenation etc.) according to desired water quality benchmark.The excess sludge that adopts this biological processes method to produce can adopt method of the present invention to carry out wet oxidation and handle.
For example handle the remaining NH of having in the water
4During-N, as described below, utilize the denitrification reaction of denitrifier under nitration reaction by utilizing nitrobacteria under the aerobic conditions and the oxygen free condition, carry out biological processes to handling water.
In addition, handle and remaining in the water (NO to be arranged
2+ NO
3During)-N, can make NO
2Carry out nitration reaction and denitrification reaction and generate NO
3
Because this biological processes method is known technology, in the present invention without limits, normally carry out under 30 ℃ the condition in pH7.5～8, temperature.
In addition, the excess sludge that adopts above-mentioned biological processes method to produce can be recycled in the former water pot, adopts wet oxidation processing method of the present invention and waste water together to handle.
In addition, the regeneration treatment fluid of reaction tower catalyst filling used in the present invention can be handled the metal ingredient of removing in the liquid by coagulation sedimentation where necessary, also can adopt method of the present invention afterwards, together carries out wet oxidation with waste water and handles.The regeneration of this catalyst is not special to be limited, gas-liquid mixed that for example can be by using acidic aqueous solution and air mutually and/or the gas-liquid mixed carrying out washing treatment mutually of alkaline aqueous solution and air make it to regenerate.Acidic aqueous solution is aqueous solution of nitric acid, aqueous ascorbic acid etc. for example, and alkaline aqueous solution for example is sodium hydrate aqueous solution, potassium hydroxide aqueous solution etc.
According to the present invention, when the waste water that contains at least a nitrogen-containing compound, organic substance and inorganic substances (dirty composition) being carried out the wet oxidation processing, because the part of the high-temperature liquid-phase that obtains by gas-liquid separation after wet oxidation is handled is carried out heat recirculation, keep liquidus speed in the tower, even the occasion of using relatively large air (oxygen) or oxygen-containing gas and under high temperature, condition of high voltage, handling, do not need external heat yet, and can keep good liquid phase state, continue reaction.
And, according to the present invention,, reduce the liquid-film resistance of catalyst surface simultaneously owing to can reduce the amount of metal ingredient attached to catalyst surface, therefore can improve catalyst activity and durability, be not subjected to the restriction of dirty constituent concentration, effectively handle waste water.
And according to the present invention, because each step can be implemented continuously, handling process is very simple, so significantly reduction of processing cost (installation cost, traffic expense etc.), and process management simultaneously also becomes easy.
And, according to the 2nd processing method of the present invention, at 10kg/cm
2(0.98MPa) under the following comparatively gentle pressure waste water carried out the short time wet oxidation and finishes dealing with after, can be by remaining COD in the activated sludge process resolution process water, and can be by remaining NH in the biology denitrogenation processing resolution process water
4-N and/or (NO
2+ NO
3)-N.
And, according to the 2nd processing method, when using the high gas (for example pure oxygen) of oxygen concentration, at 10kg/cm
2Under the lower pressure condition (0.98MPa), can carry out wastewater treatment to be divided into chronomere.
And, according to the 1st processing method, use the gas that contains aerobic, when under subcritical, critical or super critical condition, carrying out wastewater treatment, can with the second chronomere's end operation.
II. relate to the invention of catalyst washing regeneration method
When usually under the hot conditions more than 100 ℃, waste water being carried out wet oxidation and handles, if use catalyst, because the chemical erosion of the catalyst metals that the separating out of dirty composition and catabolite thereof, precipitation, catabolite cause in the waste water, and the variation of the chemistry of catalyst metals surface microscopic and physical property, cause catalyst activity to reduce gradually.The particularly chemistry on catalyst metals surface and change in physical, with observedly easily separate out by microscope etc., precipitate, phenomenon such as erosion is different, this variation is difficult to hold, and it be not immediately clear it is how what material produces harmful effect to catalyst activity in addition.But, can infer that the chemistry of this catalyst surface and change in physical are because equal or cause than its more serious catalyst activity inhibition factor with the erosion of catalyst surface etc.Adopt method of the present invention, carry out the catalyst of carrying out washing treatment under gas-liquid mixed phase state, its activity can return to and adopt the catalyst after the method for first to file is handled identical or higher.Particularly according to the kind of the waste water of handling, the composition of catalyst etc., regenerate under optimum condition when handling, its activity almost can return to the degree roughly the same with raw catelyst.
Adopt the inventive method to carry out the wastewater oxidation catalyst of regenerated from washing, its catalyst activity composition contains at least a in the water-insoluble of chosen from Fe, cobalt, nickel, magnesium, ruthenium, rhodium, palladium, iridium, platinum, copper, gold and tungsten and these metals and even the insoluble chemical compound.Compound insoluble to water or indissoluble for example is oxides such as (i) di-iron trioxide, tri-iron tetroxide, cobalt black, nickel monoxide, ruthenic oxide, rhodium sesquioxide, palladium monoxide, iridium dioxide, cupric oxide, tungsten dioxide, (ii) chloride such as ruthenic chloride, platinum chloride (iii) vulcanizes ruthenium, rhodium sulphide sulfides etc.
The present invention comprises multiple mode according to the regeneration of catalyst with cleaning solution, below detailed respectively explanation variety of way.
I. the 1st kind of mode of the present invention, the wastewater oxidation catalyst that under the condition of bubbling air, uses acidic aqueous solution washing catalytic activity to reduce.
Acidic aqueous solution preferably uses aqueous solution of nitric acid, aqueous ascorbic acid etc.The concentration of acidic aqueous solution is different according to wastewater oxidation activity of such catalysts reduction degree etc., is generally more than the 1 weight %, more preferably 5～10 weight %.
The amount of bubbling air is with respect to cleaning solution 1m
3/ hr is 10Nm
3More than/the hr, more preferably 10～100Nm
3/ hr.
The condition of washes oxidation catalyst can wait to determine according to the kind and the concentration of the degree of catalyst activity reduction, the kind of catalyst, the degree that requires the catalyst activity recovery, cleaning solution under gas-liquid mixed phase state, not special the qualification normally carried out (more preferably 30～180 minutes) more than 15 minutes under the temperature of (more preferably 40～90 ℃) more than normal temperature=20 ℃.Pressure during washing can be atmospheric pressure, there is no need pressurization, but also can carry out under pressurized conditions.
The carrying out washing treatment of wastewater oxidation catalyst can be under the state that the reaction tower that carries out the waste water wet oxidation shuts down, and bubbling air and cleaning solution carry out.Particularly when using 2 above waste water wet oxidations processing to use reaction tower, need not stop wastewater treatment, the wastewater oxidation catalyst in several reaction towers can hocket to regenerate and handle.
Perhaps also can from reaction tower, take out catalyst, handle in the other treatment trough of packing into.
Catalyst after washing finishes can wash with water in case of necessity, utilizes afterwards again.In addition, when washing 1 catalyst activity and can not fully recover, can repeatedly carry out identical regenerated from washing and handle.
II. dual mode of the present invention, the wastewater oxidation catalyst that under the condition of bubbling air, uses alkaline aqueous solution washing catalytic activity to reduce.
Alkaline aqueous solution preferably uses sodium hydrate aqueous solution, potassium hydroxide aqueous solution etc.More preferably sodium hydrate aqueous solution wherein.The concentration of alkaline aqueous solution is different according to wastewater oxidation activity of such catalysts reduction degree etc., is generally more than the 1 weight %, more preferably 5～10 weight %.
When washing with alkaline aqueous solution, the amount of bubbling air, wash conditions, washing methods, wash with water in case of necessity, drying, cyclic washing etc. be all identical when washing with acidic aqueous solution.
III. the 3rd kind of mode of the present invention behind the wastewater oxidation catalyst that uses acidic aqueous solution washing catalytic activity to reduce under the condition of bubbling air, used the alkaline aqueous solution washing again under the condition of bubbling air.In this 2 step washing methods, when washing with alkaline aqueous solution when washing with acidic aqueous solution the amount of bubbling air, wash conditions, washing methods, in case of necessity carry out repeatedly water washing, drying, washing etc. respectively with above-mentioned the 1st kind of mode and the 2nd kind of mode in identical.
IV. the 4th kind of mode of the present invention behind the wastewater oxidation catalyst that uses alkaline aqueous solution washing catalytic activity to reduce under the condition of bubbling air, used the acidic aqueous solution washing again under the condition of bubbling air.In this 2 step washing methods, when washing with alkaline aqueous solution when washing with acidic aqueous solution the amount of bubbling air, wash conditions, washing methods, in case of necessity carry out repeatedly water washing, drying, washing etc. respectively with above-mentioned the 1st kind of mode and the 2nd kind of mode in identical.
V. in addition, the scrub raffinate that produces in the above-mentioned the 1st～4 the embodiment, after for example can carrying out Separation of Solid and Liquid, its liquid phase and waste water are together carried out known wet oxidation processing (for example " the waste water wet type catalytic oxidation processing method " of the invention described above people proposition) by the coagulation sedimentation processing.At this moment, so long as relate to liquid phase, all can carry out cross processing from waste water.
Can reach following remarkable result according to the present invention.
(a) owing to can eliminate the factor that catalyst activity reduces significantly by shirtsleeve operation, the wastewater oxidation activity of such catalysts can return to the degree that can utilize again.
(b) select the suitableeest regeneration treatment conditions according to catalyst, the activity of regeneration rear catalyst can return to the degree that is equal to mutually with raw catelyst.
(c) owing to can carry out using and regenerating of catalyst repeatedly, can significantly increase the entire life of catalyst.
(d) because the needed catalyst costs of wastewater treatment reduces, can reduce the wastewater treatment expense.
(e) particularly when using 2 above waste water wet oxidations to handle use reaction tower, need not stop wastewater treatment, the regeneration that hockets of the wastewater oxidation catalyst of deterioration in several reaction towers is handled, so do not needed the taking-up of catalyst and the labour such as recharge.
(f), can reach the effect that prevents these machine obturations, prevents thermal conductivity factor reduction etc. owing to also can wash the metal ingredient of removing attached on the heat exchanger in the waste water wet oxidation equipment, gas-liquid separation device, cooler, the various pipe arrangements etc. simultaneously.
Further specify feature of the present invention below in conjunction with embodiment and comparative example.
Embodiment 1A～2A and comparative example 1A～2A
According to flow process shown in Figure 1, adopt the 1st processing method, handle the coal gas liquid (containing nitrogen-containing compound, organic substance and inorganic substances) of coke-fired furnace factory generation with the described proterties of table 1.
Table 1
| pH | 9.5 |
| COD | 6500mg/l |
| NH 4-N | 2600mg/l |
| T-N | 2900mg/l |
Embodiment 1A: with coal gas liquid supply response tower, superficial linear velocity in a column is 4hr in the tower
-1Liquidus speed is that 0.71cm/sec, mass velocity are 25.5m in (is benchmark with the void tower volume), the tower
3/ m
2Hr, the while air supply, superficial linear velocity in a column is 80.4hr
-1(converting) by standard state.The air quantity delivered is equivalent to 1.1 times of theoretical oxygen amount.In addition, fill spheric catalyst (the about 5mm of diameter) in the reaction tower, this spheric catalyst is carrier with the titanium oxide, and load has the ruthenium of vehicle weight 2%, remains on 250 ℃ of temperature and pressure 70kg/cm simultaneously
2Under the G.
The treatment fluid that reaction tower is obtained imports the 1st gas-liquid separator, carry out gas-liquid separation, the part (identical with the gas-liquid amount of supplying with) of gained liquid phase is carried out heat recirculation with reaction tower, with heat exchanger the gas-liquid that the 1st gas-liquid separator obtains is carried out recuperation of heat mutually simultaneously, with after the cooler cooling, in a row go out gas and handle water then with the 2nd gas-liquid separator separates.
The composition of the processing water that the reaction beginning obtained after 100 hours is as shown in table 2.
In addition, in present embodiment 1A, turn round after 8000 hours, handle COD and NH in the water
4The not enough 10mg/l of-N.
Embodiment 2A: the quantitative change of heat extraction recirculated liquid becomes beyond 1/2, carries out the wet oxidation of coal gas liquid according to the method for embodiment 1A and handles.But because heat recirculation liquid measure reduces by half, superficial linear velocity in a column is 3hr in the tower that closes with the coal gas liquid phase
-1Liquidus speed is that 0.53cm/sec, mass velocity are 19.1m in (is benchmark with the void tower volume), the tower
3/ m
2Hr.
The composition of the processing water that the reaction beginning obtained after 100 hours is as shown in table 2.
Comparative example 1A: except that not carrying out heat recirculation, carry out the wet oxidation of coal gas liquid according to the method for embodiment 1A and handle.But owing to omitted hot recirculation, superficial linear velocity in a column is 2hr in the tower that closes with the coal gas liquid phase
-1Liquidus speed is that 0.35cm/sec, mass velocity are 12.7m in (is benchmark with the void tower volume), the tower
3/ m
2Hr.
The composition of the processing water that the reaction beginning obtained after 100 hours is as shown in table 2.
Comparative example 2A: except that changing the reaction tower diameter, carry out the wet oxidation of coal gas liquid according to the method for embodiment 1A and handle.But because the change of reaction tower diameter, superficial linear velocity in a column is 2hr in the tower that closes with the coal gas liquid phase
-1Liquidus speed is that 0.088cm/sec, mass velocity are 3.2m in (is benchmark with the void tower volume), the tower
3/ m
2Hr.
The composition of the processing water that the reaction beginning obtained after 100 hours is as shown in table 2.
Table 2
| COD(mg/l) | NH 4-N(mg/l) | |
| Embodiment 1A | 1.8 | ＜1 |
| Embodiment 2A | 5.5 | ＜1 |
| Comparative example 1A | 11 | ＜1 |
| Comparative example 2A | 26 | 2.5 |
By result shown in the table 2 as can be seen, by carrying out heat recirculation, can improve liquidus speed in the tower, reduce the liquid-film resistance of catalyst surface, simultaneously owing to can suppress metal ingredient attached to catalyst surface, can the higher catalyst activity of long term maintenance, improve the water quality of handling water.
In addition, the time embodiment 1A that reaches with embodiment 2A same treatment water quality is 450 hours, and embodiment 2A is 340 hours, and comparative example 1A is 200 hours.
In addition, in any of embodiment 1A～2A and comparative example 1A～2A, in discharging gas (gas phase), all do not detect NO
x, SO
xAnd NH
4-N.
Embodiment 3A～12A
Except that the combination that changes catalyst component and carrier,, carry out gas-liquid and handle according to the method identical with embodiment 1A.The composition of the processing water that the reaction beginning obtained after 100 hours is as shown in table 3.
Table 3
| Catalyst | COD(mg/l) | NH 4-N(mg/l) | |
| Embodiment 3A | 1％Ir-TiO 2 | 2.9 | ＜1 |
| Embodiment 4A | 0.5％Pt-TiO 2 | 2.1 | ＜1 |
| Embodiment 5A | 1％Au-TiO 2 | 3.0 | ＜1 |
| Embodiment 6A | 0.5％Pd-TiO 2 | 1.9 | ＜1 |
| Embodiment 7A | 1％Rh-TiO 2 | 1.9 | ＜1 |
| Embodiment 8A | 5％Fe-TiO 2 | 4.5 | 2.5 |
| Embodiment 9A | 5％Ni-TiO 2 | 4.0 | 1.5 |
| Embodiment 10A | 5％W-TiO 2 | 7.8 | 4.9 |
| Embodiment 11A | 5％Cu-TiO 2 | 2.1 | 4.0 |
| Embodiment 12A | 5％Co-ZrO 2 | 2.1 | ＜1 |
Embodiment 13A
According to flow process shown in Figure 1,, the scrubber waste water that produces in the coal gasification engineering is passed in the tower that is filled with ion exchange resin according to the 1st processing method, after absorption removes the deammoniation composition, handle with the waste water (pH=6.6, COD=1.9mg/l, the NH that contain ammonia behind the aqueous sulfuric acid desorption
4-N=2100mg/l, T-N=2100mg/l).
That is to say that with above-mentioned waste water supply response tower, superficial linear velocity in a column is 8hr in the tower
-1Liquidus speed is that 0.88cm/sec, mass velocity are 31.8m in (is benchmark with the void tower volume), the tower
3/ m
2Hr, the air (oxygen concentration is 90%) that oxygen is rich in supply simultaneously is as oxygen-containing gas, and superficial linear velocity in a column is 13.4hr
-1(converting) by standard state.The quantity delivered of oxygen-containing gas is equivalent to 1.5 times of theoretical oxygen amount.In addition, fill spheric catalyst (the about 1.5mm of diameter) in the reaction tower, this spheric catalyst is carrier with the titanium oxide, and load has the ruthenium of vehicle weight 2.3%, keeps 200 ℃ of temperature and pressure 20kg/cm simultaneously
2G.
The treatment fluid that reaction tower is obtained imports the 1st gas-liquid separator, carry out gas-liquid separation, the part (identical with the wastewater flow rate of supplying with) of gained liquid phase is carried out heat recirculation with reaction tower, after the gas phase cooling of heated waste water being used with cooler, in a row go out gas and processing water with the 2nd gas-liquid separator separates.
The composition of the processing water that the reaction beginning obtained after 100 hours is as shown in table 4.
Embodiment 14A
Temperature when removing (i) reaction is 170 ℃, and pressure is 9.9kg/cm
2G, (ii) liquid air tower speed (is benchmark with the void tower volume) is 4hr in the reaction tower
-1(being catalyst loading 2 times for embodiment 13A) (iii) adds 48%NaOH in advance in waste water, its pH is adjusted to 9.7, and (iv) the superficial linear velocity in a column of oxygen-containing gas is 6.7hr
-1In addition, according to the method identical, handle the waste water that contains ammonia with embodiment 13A.The composition of the processing water that the reaction beginning obtained after 100 hours is as shown in table 4.
Embodiment 15A
Removing the interior liquid air tower speed (is benchmark with the void tower volume) of (i) reaction tower is 2hr
-1(be the catalyst loading for embodiment 14 2 times) and (ii) the superficial linear velocity in a column of oxygen-containing gas (is benchmark with the void tower volume) be 3.4hr
-1In addition, according to the method identical, handle the waste water that contains ammonia with embodiment 13A.The composition of the processing water that the reaction beginning obtained after 100 hours is as shown in table 4.
In addition, fill below the position 2/3 position at the reaction tower catalyst in the present embodiment and add decomposing N H
41.1 times H of the required theoretical amount of-N=120mg/l
2O
2, can obtain result much at one with embodiment 14A.
Embodiment 16A
Except that in waste water, adding 48%NaOH in advance, its pH is adjusted to beyond 11.5, according to the method identical, handle the waste water that contains ammonia with embodiment 15A.The composition of the processing water that the reaction beginning obtained after 100 hours is as shown in table 4.
Table 4
| COD (mg/l) | NH 4-N (mg/l) | (NO 2+NO 3)-N (mg/l) | T-N (mg/l) | |
| Embodiment 13A | 1.0 | ＜1 | ＜1 | ＜1 |
| Embodiment 14A | 1.2 | ＜1 | ＜5 | ＜5 |
| Embodiment 15A | 1.6 | 120 | ＜5 | 120 |
| Embodiment 16A | 1.1 | ＜1 | 150 | 150 |
Embodiment 17A
Treatment temperature and the processing pressure removed ammonia-containing water are set at respectively above critical-temperature (374 ℃) and critical pressure (220kg/cm
2) 380 ℃ and 230kg/cm
2, liquid air tower speed (is benchmark with the void tower volume) is 240hr in the reaction tower
-1(be the catalyst loading for embodiment 13A 1/62.5) in addition, according to the method identical with embodiment 13A, handles the waste water that contains ammonia.The composition of the processing water that the reaction beginning obtained after 100 hours is as shown in table 5.
Comparative example 3A
The treatment temperature of removing ammonia-containing water is 630 ℃, does not use beyond the catalyst, according to the method identical with embodiment 17A, handles the waste water that contains ammonia.The composition of the processing water that the reaction beginning obtained after 100 hours is as shown in table 5.
Table 5
| COD (mg/l) | NH 4-N (mg/l) | (NO 2+NO 3)-N (mg/l) | T-N (mg/l) | |
| Embodiment 17A | 1.0 | ＜1 | ＜1 | ＜1 |
| Comparative example 3A | 1.9 | 110 | 25 | 135 |
Embodiment 18A
According to flow process shown in Figure 1, adopt the 1st processing method, handle the waste water that contains organic substance (pH=2.6, COD=28100mg/l, TOD=101800mg/l, TOC=36500mg/l, NH that petrochemical plant obtains
4The not enough 1mg/l of-N, the not enough 1mg/l of T-N).Organic substance in the waste water is acetate, acrylic acid, formaldehyde, formic acid etc.
That is to say that with above-mentioned waste water supply response tower, superficial linear velocity in a column is 2.9hr in the tower
-1Liquidus speed is that 0.71cm/sec, liquid mass velocity are 25.5m in (is benchmark with the void tower volume), the tower
3/ m
2Hr, air supply is as oxygen-containing gas simultaneously, and superficial linear velocity in a column is 553hr
-1(converting) by standard state.The air quantity delivered is equivalent to 1.5 times of theoretical oxygen amount.In addition, fill spheric catalyst (the about 5mm of diameter) in the reaction tower, this spheric catalyst is carrier with the titanium oxide, and load has the ruthenium of vehicle weight 1.5%, keeps 270 ℃ of temperature and pressure 90kg/cm simultaneously
2G.
The treatment fluid that reaction tower is obtained imports the 1st gas-liquid separator, carry out gas-liquid separation, the part (identical with the gas-liquid amount of supplying with) of gained liquid phase is carried out heat recirculation with reaction tower, after the gas phase cooling of heated waste water being used with cooler, in a row go out gas and processing water with the 2nd gas-liquid separator separates.
In the present embodiment, can pressure recovery be 24kg/cm in the outlet of reactor
2Steam 0.84ton/hr.
The composition of the processing water that the reaction beginning obtained after 100 hours is as shown in table 4.
Comparative example 4A
Except that not carrying out heat recirculation,, carry out the wet oxidation of waste water and handle according to the method identical with embodiment 18A.But owing to omitted hot recirculation, superficial linear velocity in a column is 1.5hr in the tower relevant with waste water
-1Liquidus speed is that 0.35cm/sec, mass velocity are 12.7m in (is benchmark with the void tower volume), the tower
3/ m
2Hr.
The composition of the processing water that the reaction beginning obtained after 100 hours is as shown in table 6.
Table 6
| COD (mg/l) | TOC (mg/l) | NH 4-N (mg/l) | T-N (mg/l) | |
| Embodiment 18A | ＜3 | ＜5 | ＜1 | ＜1 |
| Comparative example 4A | 28.1 | 12 | ＜1 | ＜1 |
In addition, the time embodiment 18A that reaches with comparative example 4A same treatment water quality is 350 hours.
In addition, in any of embodiment 18A and comparative example 4A, in discharging gas (gas phase), all do not detect NOx, SOx and NH
4-N.
And, among the embodiment 18A, turn round after 8000 hours, handle COD and the also not enough 10mg/l of TOD in the water.
Embodiment 1B～2B and comparative example 1B～2B
According to flow process shown in Figure 2, adopt method of the present invention, handle the coal gas liquid (containing nitrogen-containing compound, organic substance and inorganic substances) of coke-fired furnace factory generation with the described proterties of table 7.
Table 7
| pH | 9.5 |
| COD | 6500mg/l |
| NH 4-N | 2600mg/l |
| T-N | 2900mg/l |
Embodiment 1B: with coal gas liquid supply response tower, superficial linear velocity in a column is 8hr in the tower
-1Liquidus speed is that 0.71cm/sec, mass velocity are 25.5m in (is benchmark with the void tower volume), the tower
3/ m
2Hr supplies with oxygen concentration and is 92.5% high-purity oxygen-containing gas (with the air compression, improving the gas of oxygen concentration with the PSA device) simultaneously, and superficial linear velocity in a column is 24.9hr
-1(converting) by standard state.Gas delivery volume is equivalent to 1.5 times of theoretical oxygen amount.In addition, fill spheric catalyst (the about 5mm of diameter) in the reaction tower, this spheric catalyst is carrier with the titanium oxide, and load has the ruthenium of vehicle weight 2%, keeps 250 ℃ of temperature and pressure 46kg/cm simultaneously
2G.
The treatment fluid that reaction tower is obtained imports the 1st gas-liquid separator, carry out gas-liquid separation, the part (identical with the gas-liquid amount of supplying with) of gained liquid phase is carried out heat recirculation with reaction tower, with heat exchanger the gas-liquid that the 1st gas-liquid separator obtains is carried out recuperation of heat mutually simultaneously, with after the cooler cooling, in a row go out gas and handle water then with the 2nd gas-liquid separator separates.
Then, gained is handled water and carry out the biology denitrogenation processing.The biology denitrogenation processing is 2.5 times the methyl alcohol that adds remaining ammonia molal quantity in handling water, carries out successively by the nitration reaction of utilizing nitrobacteria and the denitrification reaction that utilizes denitrifying bacteria under 30 ℃, the condition of pH7.2.
The composition of wet oxidation processing water that the reaction beginning obtained after 100 hours and denitrogenation processing water (numerical value in the bracket) is as shown in table 8.
In addition, in present embodiment 1B, turn round after 8000 hours COD in the denitrogenation processing water and NH
4The not enough 10mg/l of-N.
Embodiment 2B: the quantitative change of heat extraction recirculated liquid becomes beyond 1/2, carries out the wet oxidation of coal gas liquid according to the method for embodiment 1B and handles.But because heat recirculation liquid measure reduces by half, superficial linear velocity in a column is 6hr in the tower that closes with the coal gas liquid phase
-1Liquidus speed is that 0.53cm/sec, mass velocity are 19.1m in (is benchmark with the void tower volume), the tower
3/ m
2Hr.
The composition of the processing water that the reaction beginning obtained after 100 hours is as shown in table 8.
Comparative example 1B: except that not carrying out heat recirculation, carry out the wet oxidation of coal gas liquid according to the method for embodiment 1B and handle.But owing to omitted hot recirculation, superficial linear velocity in a column is 4hr in the tower that closes with the coal gas liquid phase
-1Liquidus speed is that 0.35cm/sec, mass velocity are 12.7m in (is benchmark with the void tower volume), the tower
3/ m
2Hr.
The composition of the processing water that the reaction beginning obtained after 100 hours is as shown in table 8.
Comparative example 2B: except that changing the reaction tower diameter, carry out the wet oxidation of coal gas liquid according to the method for embodiment 1B and handle.But because the change of reaction tower diameter, superficial linear velocity in a column is 4hr in the tower that closes with the coal gas liquid phase
-1Liquidus speed is that 0.088cm/sec, mass velocity are 3.2m in (is benchmark with the void tower volume), the tower
3/ m
2Hr.
The composition of the processing water that the reaction beginning obtained after 100 hours is as shown in table 8.
Table 8
| COD (mg/l) | NH 4-N (mg/l) | (NO 2+NO 3)-N (mg/l) | T-N (mg/l) | |
| Embodiment 1B | 4.0 (3.0) | ＜1 (＜1) | 45 (＜10) | 45 (＜10) |
| Embodiment 2B | 8.2 (7.0) | ＜1.2 (＜1) | 50 (＜10) | 52 (＜10) |
| Comparative example 1B | 14.0 (13.0) | ＜2.1 (＜1) | 63 (＜10) | 65 (＜10) |
| Comparative example 2B | 35.1 (30.5) | 9.1 (＜1) | 120 (＜10) | 130 (＜10) |
By result shown in the table 8 as can be seen, by carrying out heat recirculation, can improve liquidus speed in the tower, reduce the liquid-film resistance of catalyst surface, simultaneously owing to can suppress metal ingredient from waste water attached to catalyst surface, can the higher catalyst activity of long term maintenance, improve the water quality of the processing water after the wet oxidation.And, same processing water is carried out the biology denitrogenation processing, can further improve water quality.
In addition, in any of embodiment 1B～2B and comparative example 1B～2B, in discharging gas (gas phase), all do not detect NO
x, SO
xAnd NH
4-N.
In addition, reach the time with embodiment 2B same treatment water quality, embodiment 1B is 470 hours, and embodiment 2B is 365 hours, and comparative example 1B is 230 hours.
Embodiment 3B～12B
Except that the combination that changes catalyst component and carrier,, carry out gas-liquid and handle according to the method identical with embodiment 1B.
The composition of the processing water that the reaction beginning obtained after 100 hours is as shown in table 9.
Table 9
| Catalyst | COD(mg/l) | NH 4-N(mg/l) | |
| Embodiment 3B | 1％Ir-TiO 2 | 4.1 | ＜10 |
| Embodiment 4B | 0.5％Pt-TiO 2 | 3.9 | ＜10 |
| Embodiment 5B | 1％Au-TiO 2 | 3.9 | ＜10 |
| Embodiment 6B | 0.5％Pd-TiO 2 | 1.9 | ＜10 |
| Embodiment 7B | 1％Rh-TiO 2 | 2.0 | ＜10 |
| Embodiment 8B | 5％Fe-TiO 2 | 9.4 | ＜10 |
| Embodiment 9B | 5％Ni-TiO 2 | 8.9 | ＜10 |
| Embodiment 10B | 5％W-TiO 2 | 9.4 | ＜10 |
| Embodiment 11B | 5％Cu-TiO 2 | 4.3 | ＜10 |
| Embodiment 12B | 5％Co-ZrO 2 | 2.9 | ＜10 |
Embodiment 13B
According to flow process shown in Figure 2,, the scrubber waste water that produces in the coal gasification engineering is passed in the tower that is filled with ion exchange resin according to the 2nd processing method, after absorption removes the deammoniation composition, handle with the waste water (pH=6.6, COD=1.9mg/l, the NH that contain ammonia behind the aqueous sulfuric acid desorption
4-N=2100mg/l, (NO
2+ NO
3)-N=ND, T-N=2100mg/l).
That is to say that with above-mentioned waste water supply response tower, superficial linear velocity in a column is 10hr in the tower
-1Liquidus speed is that 0.88cm/sec, mass velocity are 31.8m in (is benchmark with the void tower volume), the tower
3/ m
2Hr, the air (oxygen concentration is 95%) that oxygen is rich in supply simultaneously is as oxygen-containing gas, and superficial linear velocity in a column is 15.9hr
-1(converting) by standard state.The quantity delivered of oxygen-containing gas is equivalent to 1.5 times of theoretical oxygen amount.In addition, fill spheric catalyst (the about 1.5mm of diameter) in the reaction tower, this spheric catalyst is carrier with the titanium oxide, and load has the ruthenium of vehicle weight 2.3%, keeps 200 ℃ of temperature and pressure 20kg/cm simultaneously
2G.
The treatment fluid that reaction tower is obtained imports the 1st gas-liquid separator, carry out gas-liquid separation, the part (identical with the gas-liquid amount of supplying with) of gained liquid phase is carried out heat recirculation with reaction tower, after the gas phase of heated waste water being used with cooler is cooled off simultaneously, in a row go out gas and handle water with the 2nd gas-liquid separator separates.
According to the method identical, water is handled in the wet oxidation that obtains carried out the biology denitrogenation processing then with embodiment 1B.
The composition of the processing water that the reaction beginning obtained after 100 hours is as shown in table 10.
Embodiment 14B
Temperature when removing (i) reaction is 170 ℃, and pressure is 9.9kg/cm
2G, (ii) liquid air tower speed (is benchmark with the void tower volume) is 5hr in the reaction tower
-1(being catalyst loading 2 times for embodiment 13B) (iii) adds 48%NaOH in advance in waste water, its pH is adjusted to 9.7, and (iv) the superficial linear velocity in a column of oxygen-containing gas is 7.95hr
-1In addition, according to the method identical with embodiment 13B, the waste water that contains ammonia is handled in wet oxidation, carries out the biology denitrogenation processing then.
The composition of the processing water that the reaction beginning obtained after 100 hours is as shown in table 10.
Embodiment 15B
Except that in waste water, adding 48%NaOH in advance, its pH is adjusted to beyond 11.5, according to the method identical with embodiment 14B, the waste water that contains ammonia is handled in wet oxidation, carries out the biology denitrogenation processing then.
The composition of the processing water that the reaction beginning obtained after 100 hours is as shown in table 10.
Table 10
| COD (mg/l) | NH 4-N (mg/l) | (NO 2+NO 3)-N (mg/l) | T-N (mg/l) | |
| Embodiment 13B | 1.1 (1.0) | ＜1 (＜1) | ＜1 (＜1) | ＜1 (＜10) |
| Embodiment 14B | 1.9 (1.6) | ＜12.5 (＜10) | ＜1 (＜1) | 120 (＜10) |
| Embodiment 15B | 1.9 (1.3) | 4.5 (＜1) | 165 (＜10) | 150 (＜10) |
Comparative example 3B
Treatment temperature and the processing pressure removed ammonia-containing water are set at respectively above critical-temperature (374 ℃) and critical pressure (220kg/cm
2) 380 ℃ and 230kg/cm
2, liquid air tower speed (is benchmark with the void tower volume) is 240hr in the reaction tower
-1(be the catalyst loading for embodiment 14B 1/62.5) in addition, according to the method identical with embodiment 13B, only carried out wet oxidation to the waste water that contains ammonia and handled.The proterties of the water quality of processing water and discharge gas and the occasion of embodiment 13B are much at one.
Embodiment 16B
According to flow process shown in Figure 2, adopt the 2nd processing method, handle the waste water that contains organic substance (pH=2.6, COD=28100mg/l, TOD=101800mg/l, TOC=36500mg/l, NH that petrochemical plant obtains
4-N＜below the 1mg/l, T-N＜1mg/l is following).Organic substance in the waste water is acetate, acrylic acid, formaldehyde, formic acid etc.
That is to say that with above-mentioned waste water supply response tower, superficial linear velocity in a column is 2.9hr in the tower
-1Liquidus speed is that 0.71cm/sec, liquid mass velocity are 25.5m in (is benchmark with the void tower volume), the tower
3/ m
2Hr supplies with rich oxygen containing air (oxygen concentration is 92.5%) simultaneously as oxygen-containing gas, and superficial linear velocity in a column is 116hr
-1(converting) by standard state.The quantity delivered of rich oxygen containing gas is equivalent to 1.2 times of theoretical oxygen amount.In addition, fill spheric catalyst (the about 5mm of diameter) in the reaction tower, this spheric catalyst is carrier with the titanium oxide, and it is 1.5% platinum that load has load weight, keeps 270 ℃ of temperature and pressure 67kg/cm simultaneously
2
The treatment fluid that reaction tower is obtained imports the 1st gas-liquid separator, carry out gas-liquid separation, the part (identical with the gas-liquid amount of supplying with) of gained liquid phase is carried out heat recirculation with reaction tower, after the gas phase cooling of heated waste water being used with cooler, in a row go out gas and processing water with the 2nd gas-liquid separator separates.
Then, and employing Wastewater Treated by Activated Sludge Process gained wet oxidation processing water (about 30 ℃ of temperature, pH7.4).
The composition of the processing water that the reaction beginning obtained after 100 hours is as shown in table 11.
In the present embodiment, can in the ratio pressure recovery of 0.84ton/hr 24kg/cm in the outlet of reactor
2Steam.
Comparative example 4B
Except that not carrying out heat recirculation,, carry out the wet oxidation of waste water and handle according to the method identical with embodiment 16B.But owing to omitted hot recirculation, superficial linear velocity in a column is 1.5hr in the tower relevant with waste water
-1Liquidus speed is that 0.35cm/sec, mass velocity are 12.7m in (is benchmark with the void tower volume), the tower
3/ m
2Hr.
The composition of the processing water that the reaction beginning obtained after 100 hours is as shown in table 11.
Table 11
| COD (mg/l) | TOC (mg/l) | NH 4-N (mg/l) | T-N (mg/l) | |
| Embodiment 16B | ＜3 (1.8) | ＜5 (＜5) | ＜1 (＜1) | ＜1 (＜1) |
| Comparative example 4B | 275 (＜13) | ＜15 (＜10) | ＜1 (＜1) | 1 (＜1) |
By result shown in the table 11 as can be seen, by carrying out heat recirculation, can improve liquidus speed in the tower, reduce the liquid-film resistance of catalyst surface, simultaneously owing to can suppress metal ingredient from waste water attached to catalyst surface, can the higher catalyst activity of long term maintenance, improve the water quality of wet oxidation post processing water.And, same processing water is carried out biological processes, can further improve water quality.
In addition, in any of embodiment 16B and comparative example 4B, in discharging gas (gas phase), all do not detect NOx, SOx and NH
4-N.
And, among the embodiment 16B, turn round after 8000 hours, handle COD and the not enough 10mg/l of TOD in the water.
Embodiment 1C～8C
(1) wet oxidation of waste water is handled
At first the coal gas liquid that produces in the STRENGTH ON COKE stove (COD6000ppm, total ammonia amount 3000ppm, nitrogen pool 4000ppm) carries out the wet oxidation processing.
That is to say, in coal gas liquid, add sodium hydrate aqueous solution, its pH is adjusted to about 10, with space velocity 1.0hr
-1(is benchmark with the void tower) supplies with the bottom of cylinder reactor.The mass velocity of liquid is 8.0m
3/ m
2Hr.
On the other hand, in the bottom of reaction tower with space velocity 65hr
-1(with the void tower is benchmark, standard state) air supply.
In reaction tower, fill spherical wastewater oxidation catalyst (the about 5mm of diameter) with the described composition of following table 12.In table 12,1%Ir-TiO
2Be meant the catalyst of load iridium 1 weight % on titanium dioxide carrier.
In addition, the coal gas liquid of use contained iron, calcium and the magnesium that amounts to 15ppm originally, in order to make effect of the present invention clearer and more definite, added the compound that contains these elements in advance and made its total amount reach 2500ppm.
In the wet oxidation of coal gas liquid is handled, inner 250 ℃ of temperature, the pressure 70kg/cm of keeping of reaction tower
2G adds pH that sodium hydrate aqueous solution makes wet oxidation handle aftertreatment fluid and reaches about 7.5, and sustained response is 5000 hours simultaneously.The activity of such catalysts index reduces as a result, and is as shown in table 12.The precipitate on analysis of catalyst surface confirms to exist sulphur and ash content (silica, iron oxide, magnesia, other) etc., does not detect carbon, hydro carbons etc.
(2) the regeneration carrying out washing treatment of catalyst
Then, adopt following the whole bag of tricks to the processing of regenerating of the wastewater oxidation catalyst of activity reduction.
* method-1: under atmospheric pressure in the reaction tower that is filled with the wastewater oxidation catalyst, feed 10% aqueous solution of nitric acid (80 ℃), wash after 1 hour, wash 1 hour with water.The feeding condition of aqueous solution of nitric acid and water during with wastewater treatment the feeding condition of waste water identical.
* method-2: under atmospheric pressure bubbling air and 10% aqueous solution of nitric acid (80 ℃) in the reaction tower that is filled with the wastewater oxidation catalyst, wash after 1 hour, wash 1 hour with water.The feeding condition of aqueous solution of nitric acid and air during respectively with wastewater treatment the feeding condition of waste water and air identical.That is, with respect to aqueous solution of nitric acid 1m
3/ hr, air feeding amount is 65Nm
3/ hr.
The feeding condition of waste water was identical when the feeding condition of water was with wastewater treatment when washing with water in addition.
* method-3: under atmospheric pressure in the reaction tower that is filled with the wastewater oxidation catalyst, feed 10% sodium hydrate aqueous solution (80 ℃), wash after 1 hour, wash 1 hour with water.The feeding condition of sodium hydrate aqueous solution and water during with wastewater treatment the feeding condition of waste water identical.
* method-4: under atmospheric pressure bubbling air and 10% sodium hydrate aqueous solution (80 ℃) in the reaction tower that is filled with the wastewater oxidation catalyst, wash after 1 hour, wash 1 hour with water.The feeding condition of sodium hydrate aqueous solution and air during with wastewater treatment the feeding condition of waste water and air identical respectively.That is, with respect to sodium hydrate aqueous solution 1m
3/ hr, air feeding amount is 65Nm
3/ hr.
The feeding condition of waste water was identical when the feeding condition of water was with wastewater treatment when washing with water in addition.
Table 12
| Embodiment | Catalyst is formed | Activity index before the regeneration | Method 1 activity index | Method 2 activity indexs | Method 3 activity indexs | Method 4 activity indexs |
| 1C | 1％Ir-TiO 2 | 65 | 73 | 93 | 83 | 98 |
| 2C | 1％Pt-TiO 2 | 67 | 74 | 93 | 84 | 99 |
| 3C | 1％Au-AlO 2 | 54 | 69 | 88 | 74 | 94 |
| 4C | 5％Ni-AlO 2 | 54 | 68 | 87 | 73 | 95 |
| 5C | 5％W-AlO 2 | 66 | 69 | 88 | 72 | 96 |
| 6C | The 2%Pd-active carbon | 67 | 71 | 94 | 87 | 99 |
| 7C | The 1%Pt-active carbon | 63 | 69 | 92 | 79 | 99 |
| 8C | 2％Ru-TiO 2 | 69 | 84 | 97 | 93 | 100 |
In the table 12, " activity index " is meant that using raw catelyst is to the occasion ammonia clearance rate that waste water carries out the wet oxidation processing at 100% o'clock, uses regenerated catalyst waste water to be carried out the clearance rate of the occasion ammonia of wet oxidation processing under the same conditions.Confirm that regenerated catalyst is for removing COD and removing the identical rising that also shows activity index of ammonia.
Under the condition of bubbling air, the wastewater oxidation catalyst is carried out regenerated from washing excellent results of the present invention when handling as can be seen by result shown in the table 12 with acidic aqueous solution or alkaline aqueous solution.
Comparative example 1C
Use the catalyst identical, under the condition identical, coal gas liquid is carried out wet oxidation handle with embodiment 1 with embodiment 1C.
Then, use the cleaning solution of 2N aqueous sulfuric acid, adopt method-1 and method-2 among the embodiment 1C to carry out catalyst regeneration as catalyst.The result is as shown in table 13.
Table 13
| Comparative example | Catalyst is formed | Activity index before the regeneration | Method 1 activity index | Method 2 activity indexs |
| 1C | 1％Ir-TiO 2 | 65 | 66 | 67 |
By result shown in the table 13 as can be seen, when using aqueous sulfuric acid, can not fully reach the regeneration effect of catalyst as cleaning solution.
Comparative example 2C
Use the catalyst identical, under the condition identical, coal gas liquid is carried out wet oxidation handle with embodiment 2C with embodiment 2C.
Use 10% aqueous solution of nitric acid then, the regenerated from washing that method-1 among the employing embodiment 2C and method-2 are carried out catalyst.But in method-2, with respect to cleaning solution 1m
3/ hr air feeding amount is 5Nm
3/ hr.The result is as shown in table 14.
Table 14
| Comparative example | Catalyst is formed | Activity index before the regeneration | Method 1 activity index | Method 2 activity indexs |
| 2C | 1％Pt-TiO 2 | 67 | 74 | 77 |
By result shown in the table 14 as can be seen, when the gas-liquid mixed phase being washed,, can not fully reach the regeneration effect of catalyst if air feeding amount is very few by aqueous solution of nitric acid and air.
Embodiment 9C
(1) wet oxidation of waste water is handled
At first, use not the 1st secondary response tower and the 2nd secondary response tower that is filled with catalyst of catalyst filling, carry out the wet oxidation processing having the waste liquid of forming shown in the table 15 that contains the cyanogen complex ion (pH10.6).
Table 15
| Composition | Concentration (mg/l) |
| Always-CN | 10000 |
| CODMn | 15000 |
| TOC | 5000 |
| TOD | 30240 |
| Always-N | 8000 |
| NH 3-N | 2615 |
| Na | 25000 |
| K | 15000 |
| Fe | 2000 |
| Zn | 145 |
| P | 240 |
| Al | 1.3 |
| Cu | 5.4 |
That is to say, with space velocity 1.0hr
-1(is benchmark with the void tower) and mass velocity 14.15m
3/ m
2Hr supplies with the 1st secondary response tower bottom with waste liquid, in the 1st secondary response tower bottom with space velocity 3.4hr
-1(with the void tower is benchmark, standard state) air supply.The air quantity delivered is equivalent to theoretical oxygen amount (82.5Nm
3/ kl) 0.0103 times.
During the resolution process waste liquid, entrance side at heat exchanger imports waste liquid and air, make the gas-liquid mixture temperature (the gas-liquid mixture temperature of=first set reaction tower entrance side) of heat exchanger outlet side reach 150 ℃, the part of the treatment fluid that will come out from the 2nd secondary response tower by pump is mixed the adjustment temperature with the treatment fluid circulation of coming out from the first set reaction tower.In addition, in the first set reaction tower,, make to keep 220 ℃ of temperature, pressure 30kg/cm in the tower by supplying with steam
2In addition, the 70cm place is being installed by the column plate type reaction tower at interval with the first set reaction tower.
In the liquid (pH10.6) after the 1st secondary response tower is handled, the metal ingredient in the waste liquid had become mud originally, was discharged by reaction tower bottom and solid-liquid separator (film punching press) bottom.Forming of the 1st treatment fluid that is obtained by solid-liquid separator is shown in table 16.
Table 16
| Composition | Concentration (mg/l) |
| Always-CN | 0.1 |
| CODMn | 1445 |
| TOC | 5000 |
| TOD | 25300 |
| Always-N | 6690 |
| NH 3-N | 6900 |
| Na | 20900 |
| K | 12540 |
| Fe | 47 |
| Zn | 20 |
| P | 145 |
| Al | ＜0.5 |
| Cu | 3.5 |
Then, after in first time treatment fluid, adding the 0.62ml sulfuric acid that is equivalent to alkali metal content (Na0.909mol/l+K0.332mol/l=1.231mol/l) 1/2 in the treatment fluid for the first time by the sulfuric acid storage tank, with space velocity 0.75/hr (is benchmark with the void tower) and mass velocity 14.15m
3/ m
2The second time that hr is filled with catalyst with its supply is in the reaction tower, simultaneously with space velocity 90.4/hr (with the void tower is benchmark, standard state) air supply.The air quantity delivered is equivalent to 1.1 times of theoretical oxygen amount.In addition, (diameter 4～6mm), this spheric catalyst are carrier with the titanium oxide, and load has the ruthenium of vehicle weight 2% to be filled with spheric catalyst in the reaction tower in the second time.
Shown in table 17 by forming of treatment fluid (pH3.1) that the second time, reaction tower obtained.
Table 17
| Composition | Concentration (mg/l) |
| Always-CN | ＜0.01 |
| COD Mn | ＜1 |
| TOC | ＜5 |
| TOD | ＜5 |
| Always-N | 40 |
| NH 3-N | ＜1 |
| Na | 20900 |
| K | 12540 |
| Fe | 1.0 |
| Zn | 0.3 |
| P | 0.3 |
| Al | ＜0.5 |
| Cu | 0.3 |
(2) the regeneration carrying out washing treatment of catalyst
Then, adopt following the whole bag of tricks to handling for the second time after 16000 hours the processing of regenerating of the wastewater oxidation catalyst of active reduction.
* method-1: under atmospheric pressure in the reaction tower that is filled with the wastewater oxidation catalyst, feed 10% aqueous ascorbic acid (60 ℃), wash after 5 hours, wash 1 hour with water.The feeding condition of aqueous ascorbic acid and water during with wastewater treatment the feeding condition of waste water identical.
* method-2: under atmospheric pressure bubbling air and 10% aqueous ascorbic acid (60 ℃) in the reaction tower that is filled with the wastewater oxidation catalyst, wash after 5 hours, wash 1 hour with water.The feeding condition of aqueous ascorbic acid and air during with wastewater treatment the feeding condition of waste water and air identical respectively.That is, with respect to aqueous ascorbic acid 1m
3/ hr, air feeding amount is 120Nm
3/ hr.
The feeding condition of waste water was identical when the feeding condition of water was with wastewater treatment when washing with water in addition.
* method-3: under atmospheric pressure in the reaction tower that is filled with the wastewater oxidation catalyst, feed 10% aqueous solution of nitric acid (60 ℃), wash after 5 hours, wash 1 hour with water.The feeding condition of aqueous solution of nitric acid and water during with wastewater treatment the feeding condition of waste water identical.
* method-4: under atmospheric pressure bubbling air and 10% aqueous solution of nitric acid (60 ℃) in the reaction tower that is filled with the wastewater oxidation catalyst, wash after 5 hours, wash 1 hour with water.The feeding condition of aqueous solution of nitric acid and air during with wastewater treatment the feeding condition of waste water and air identical respectively.That is, with respect to aqueous solution of nitric acid 1m
3/ hr, air feeding amount is 120Nm
3/ hr.
The feeding condition of waste water was identical when the feeding condition of water was with wastewater treatment when washing with water in addition.
* method-5: under atmospheric pressure in filling, feed 10% aqueous ascorbic acid (60 ℃), washed 5 hours by the reaction tower of wastewater oxidation catalyst.Then, under atmospheric pressure bubbling air and 10% aqueous solution of nitric acid washed after 5 hours, washed 1 hour with water.The feeding condition of aqueous ascorbic acid and aqueous solution of nitric acid during with wastewater treatment the feeding condition of waste water identical, 1/2 when the feeding amount of air is wastewater treatment.That is, with respect to aqueous solution of nitric acid 1m
3/ hr, air feeding amount is 60Nm
3/ hr.
The feeding condition of waste water was identical when the feeding condition of water was with wastewater treatment when washing with water in addition.
Adopt the reproduced state of the whole bag of tricks rear catalyst shown in table 18.
Table 18
| Activity index before the regeneration | 69 |
| Method-1 is handled the back activity index | 84 |
| Method-2 is handled the back activity index | 97 |
| Method-3 is handled the back activity index | 89 |
| Method-4 is handled the back activity index | 92 |
| Method-5 is handled the back activity index | 100 |
Under the condition of bubbling air, the wastewater oxidation catalyst is carried out regenerated from washing excellent results of the present invention when handling as can be seen by the result of table 18 with acidic aqueous solution.
In addition, adopt said method-5 pair because after adhesion metal composition and heat exchanger in the waste water wet oxidation equipment that handling property reduces and pipe arrangement handle, the result compares with A-stage and has reduced about 80% the total thermal conductivity factor of heat exchanger and return to A-stage, compares with A-stage simultaneously to have increased about 1.5kg/cm
2The pipe internal pressure loss return to A-stage.
Claims (6)
1. catalyst washing regeneration method, it is characterized in that comprising the steps: to use acidic aqueous solution as cleaning solution with the washing regeneration method of supported catalyst with at least a waste water wet oxidation as the catalyst activity composition in the water-insoluble of iron, cobalt, nickel, magnesium, ruthenium, rhodium, palladium, iridium, platinum, copper, gold and tungsten and these metals and even the insoluble chemical compound, and for cleaning solution 1m
3/ hr is with 10Nm
3The ratio bubbling air that/hr is above makes catalyst contact with cleaning solution under the temperature more than the normal temperature.
2. catalyst washing regeneration method, it is characterized in that comprising the steps: to use alkaline aqueous solution as cleaning solution with the washing regeneration method of supported catalyst with at least a waste water wet oxidation as the catalyst activity composition in the water-insoluble of iron, cobalt, nickel, magnesium, ruthenium, rhodium, palladium, iridium, platinum, copper, gold and tungsten and these metals and even the insoluble chemical compound, and for cleaning solution 1m
3/ hr is with 10Nm
3The ratio bubbling air that/hr is above makes catalyst contact with cleaning solution under the temperature more than the normal temperature.
3. catalyst washing regeneration method, it is characterized in that comprising the steps: that with the washing regeneration method of supported catalyst (1) use acidic aqueous solution as cleaning solution with at least a waste water wet oxidation as the catalyst activity composition in the water-insoluble of iron, cobalt, nickel, magnesium, ruthenium, rhodium, palladium, iridium, platinum, copper, gold and tungsten and these metals and even the insoluble chemical compound, and for cleaning solution 1m
3/ hr is with 10Nm
3The ratio bubbling air that/hr is above makes catalyst contact with cleaning solution under the temperature more than the normal temperature; (2) use alkaline aqueous solution as cleaning solution, and for cleaning solution 1m
3/ hr is with 10Nm
3The ratio bubbling air that/hr is above makes catalyst contact with cleaning solution under the temperature more than the normal temperature.
4. catalyst washing regeneration method, it is characterized in that comprising the steps: that with the washing regeneration method of supported catalyst (1) use alkaline aqueous solution as cleaning solution with at least a waste water wet oxidation as the catalyst activity composition in the water-insoluble of iron, cobalt, nickel, magnesium, ruthenium, rhodium, palladium, iridium, platinum, copper, gold and tungsten and these metals and even the insoluble chemical compound, and for cleaning solution 1m
3/ hr is with 10Nm
3The ratio bubbling air that/hr is above makes catalyst contact with cleaning solution under the temperature more than the normal temperature; (2) use acidic aqueous solution as cleaning solution, and for cleaning solution 1m
3/ hr is with 10Nm
3The ratio bubbling air that/hr is above makes catalyst contact with cleaning solution under the temperature more than the normal temperature.
5. a method of wastewater treatment is characterized in that, comprises following three steps:
(1) pressure that keeps temperature more than 100 ℃ and at least a portion waste water to keep liquid phase, under the condition that supported catalyst exists, and the nitrogen-containing compound in the waste water and/or organic substance and/or inorganic substances be decomposed under the above gas that contains high purity oxygen (oxygen concentration is more than the 80%) existence condition of the necessary theoretical oxygen amount of nitrogen and/or carbon dioxide and water, the waste water that contains at least a nitrogen-containing compound, organic substance and inorganic substances is handled in wet oxidation;
(2) according to the regenerated from washing of following step (i) and/or step described supported catalyst (ii);
(i) use acidic aqueous solution as cleaning solution, and for cleaning solution 1m
3/ hr is with 10Nm
3The ratio bubbling air that/hr is above makes catalyst contact with cleaning solution under the temperature more than the normal temperature;
(ii) use alkaline aqueous solution as cleaning solution, and for cleaning solution 1m
3/ hr is with 10Nm
3The ratio bubbling air that/hr is above makes catalyst contact with cleaning solution under the temperature more than the normal temperature; And
(3) the catalyst detergent waste liquid that produces in the described step (2) is joined carry out wet oxidation in the waste water of described step (1) and handle;
Described supported catalyst, the water-insoluble of chosen from Fe, cobalt, nickel, magnesium, ruthenium, rhodium, palladium, iridium, platinum, copper, gold and tungsten and these metals or insoluble chemical compound at least a as the catalyst activity composition.
6. a method of wastewater treatment is characterized in that, comprises following four steps:
(1) pressure that keeps temperature more than 100 ℃ and at least a portion waste water to keep liquid phase, under the condition that supported catalyst exists, and the nitrogen-containing compound in the waste water and/or organic substance and/or inorganic substances be decomposed under the above gas that contains high purity oxygen (oxygen concentration is more than the 80%) existence condition of the necessary theoretical oxygen amount of nitrogen and/or carbon dioxide and water, the waste water that contains at least a nitrogen-containing compound, organic substance and inorganic substances is handled in wet oxidation;
(2) according to the regenerated from washing of following step (i) and/or step described supported catalyst (ii);
(i) use acidic aqueous solution as cleaning solution, and for cleaning solution 1m
3/ hr is with 10Nm
3The ratio bubbling air that/hr is above makes catalyst contact with cleaning solution under the temperature more than the normal temperature;
(ii) use alkaline aqueous solution as cleaning solution, and for cleaning solution 1m
3/ hr is with 10Nm
3The ratio bubbling air that/hr is above makes catalyst contact with cleaning solution under the temperature more than the normal temperature; And
(3) the catalyst detergent waste liquid that produces in the described step (2) is carried out coagulation sedimentation and handle, remove the metal ingredient in the liquid; And
(4) waste liquid of removing metal ingredient that obtains in the described step (3) is joined carry out wet oxidation in the waste water of described step (1) and handle;
Described supported catalyst, the water-insoluble of chosen from Fe, cobalt, nickel, magnesium, ruthenium, rhodium, palladium, iridium, platinum, copper, gold and tungsten and these metals or insoluble chemical compound at least a as the catalyst activity composition.
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|---|---|---|---|
| CNB001004158A CN100381371C (en) | 2000-01-31 | 2000-01-31 | Method for treating waste water and method for washing and regenerating catalyst |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001004158A Division CN100381371C (en) | 2000-01-31 | 2000-01-31 | Method for treating waste water and method for washing and regenerating catalyst |
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| Publication Number | Publication Date |
|---|---|
| CN1781606A true CN1781606A (en) | 2006-06-07 |
| CN100528362C CN100528362C (en) | 2009-08-19 |
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| JPH09253668A (en) * | 1996-03-25 | 1997-09-30 | Osaka Gas Co Ltd | Method for catalytic wet oxidation treatment of low tod waste water |
| JPH09253667A (en) * | 1996-03-25 | 1997-09-30 | Osaka Gas Co Ltd | Method for catalytic wet oxidation treatment of low tod waste water |
-
2000
- 2000-01-31 CN CNB2005101185788A patent/CN100528362C/en not_active Expired - Fee Related
- 2000-01-31 CN CNB001004158A patent/CN100381371C/en not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| CN100381371C (en) | 2008-04-16 |
| CN100528362C (en) | 2009-08-19 |
| CN1306943A (en) | 2001-08-08 |
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