CN101209883A - Technique for processing coking wastewater or organic wastewater by supercritical water oxidization technique - Google Patents
Technique for processing coking wastewater or organic wastewater by supercritical water oxidization technique Download PDFInfo
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- CN101209883A CN101209883A CNA2007103041291A CN200710304129A CN101209883A CN 101209883 A CN101209883 A CN 101209883A CN A2007103041291 A CNA2007103041291 A CN A2007103041291A CN 200710304129 A CN200710304129 A CN 200710304129A CN 101209883 A CN101209883 A CN 101209883A
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Abstract
The invention relates to a process by adopting supercritical water oxidation technology to treat coking wastewater or organic wastewater. The invention is that: coking wastewater or organic wastewater is pretreated to obtain wastewater without solid granules; the wastewater is heated to 380-450 DEG C with a first interchanger and/or a supercritical boiler, and then enters demineralizing equipment to remove the salt in the wastewater by taking advantage of the property that supercritical inorganic matter is indissoluble; the wastewater after desalting is put in a reaction kettle to generate autothermal reaction with an heated and pressurized oxidant to obtain high-temperature gas-liquid mixture with higher temperature; the high-temperature gas-liquid mixture enters the first interchanger and acts as thermal medium to exchange heat with new coming coking wastewater or organic wastewater and then goes through a secondary interchanger to enter a cooler and is cooled to normal temperature, after pressure thereof is adjusted by a pressure regulation device, the high-temperature gas-liquid mixture enters a gas-liquid separator for separation, and then the air is discharged, while the liquid, namely the treated water is recycled. The organic contamination and oxidant are all dissolved in the wastewater; oxidation reaction is generated in homogeneous phase, in short reaction time, oxygenolysis of organic contamination is carried out quickly.
Description
Technical field
The present invention relates to sewage treatment process, for example, the new technology of coking chemical waste water and other treatment of Organic Wastewater, particularly a kind of supercritical water oxidation technical finesse coking chemical waste water or organic waste water technology.
Background technology
China's coke industry development is rapid unusually, has more than 15000 coke-oven plant by the end of last year, and the coke production ability is near 300,000,000 tons.But medium and small independent coal chemical enterprise quantity accounts for more than 80% of all coking number of the enterprise, and production capacity accounts for 35%.Scope of the enterprise is little, the layout dispersion is extremely unreasonable, and the environmental protection existing problems are outstanding, noxious pollutants such as the waste water of coke production discharging, waste gas, and serious environment pollution threatens body health of people.
The at present treating coking wastewater biologicallies that adopt of the coal chemical enterprise of China more, exploitation successively and perfect " A-O, A
2-O, A-O
2Etc. technology, mainly based on activated sludge process, this method can alignment request up to standard to the processing of phenol, cyanogen, but to COD, NH
3The treatment effect of-N is often not fully up to expectations, particularly NH
3-N is not degraded almost.This process complex procedures, floor space are big, investment, working cost are also higher, and the investment of at present general coking chemical waste water denitrogenation is that ten thousand yuan of/ton water of 15-20, running cost are 5-6 unit/ton water, to take up an area of be 100-150m
2/ ton water.
In order to address this problem, set about from several respects such as microorganism, technical process and reactors, biochemical process has been carried out a large amount of research, but, also had considerable part enterprise can not satisfy the requirement of country or local environmental protection standard with regard to national situation.So the technology of physico-chemical process, burning method, catalytic wet oxidation method, supercritical water oxidation method Treatment of Wastewater in Coking or organic waste water has also caused attention in recent years, make every effort to find that one-time investment is reasonable, working cost is low, the treatment process of wide accommodation, stable water outlet.
Summary of the invention
The present invention is in order to solve the problem that traditional technology exists, a kind of supercritical water oxidation technical finesse coking chemical waste water or organic waste water technology are provided, it adopts supercritical water oxidation technical finesse coking chemical waste water or organic waste water, organic pollutant and oxygenant in the waste water all are dissolved in the water, oxidizing reaction is carried out in homogeneous phase, in the very short reaction times, organic pollutant is by rapid oxygenolysis.
Technical scheme of the present invention is as follows:
Supercritical water oxidation technical finesse coking chemical waste water or organic waste water technology is characterized in that comprising: coking chemical waste water or organic waste water are carried out pre-treatment, the waste water of the solid particulate that is removed; Waste water is by first-class heat exchanger or also by super critical boiler, enters desalination plant after being heated to 380-450 ℃, utilizes the insoluble characteristic of overcritical inorganics to remove salt in the waste water; Waste water behind the desalination is sent into reactor and the oxygenant generation autothermal reaction that passes through heating and pressurizing, obtain the higher High Temperature Gas water mixture of temperature; The High Temperature Gas water mixture enters first-class heat exchanger and is cooled to normal temperature as entering water cooler by secondary heat exchanger after thermal medium and the coking chemical waste water of newly coming in or the organic waste water heat exchange, behind regulator conciliation pressure, enter gas-liquid separator again and carry out gas-liquid separation, water cycle after gaseous emission, liquid are promptly handled is used.
The oxygenant of described heating and pressurizing is meant, enters reactor after the oxygenant in the oxygenant storage tank is pumped into the secondary heat exchanger preheating.
Described reactor adopts tubular reaction vessel.
The salt discharge outlet of described desalination plant is provided with filtering net and water flushing device, has not only prevented the obstruction of salt pair pipeline and reactor, has also realized the recycling of inorganic salt.
Described water cooler adopts the structure formation that reclaims used heat.
Described super critical boiler has just begun as primary heater, as auxiliary heater, that is: directly enters desalination plant after waste water is heated to 380-450 ℃ by first-class heat exchanger after system's operation, no longer passes through super critical boiler.
The ramp type settling tank is adopted in described pre-treatment, and adds flocculation agent to improve sedimentation effect in the ramp type settling tank.
Described tubular reaction vessel adopts the nickel based super alloy corrosion resistant material.
The described waste water of removing solid particulate pumps into first-class heat exchanger by the plunger tpe force (forcing) pump.
In the described waste water of removing solid particulate, add corrosion inhibiting and descaling agent, with fouling, the corrosion that reduces or stop heat-exchange equipment.
Technique effect of the present invention is as follows:
Adopt supercritical water oxidation technical finesse coking chemical waste water of the present invention or organic waste water technology, only need preheating, inorganic salt to separate and three reactors of oxidation, technical process is significantly shortened, and the reaction times significantly accelerates.The plant area area is the less than 1/10th of biochemical process.Pollutant discharge amount reduces tens times than general biochemical method, especially can effectively remove the condensed-nuclei aromaticss such as benzopyrene that carcinogenic potential hazard is arranged in the waste water.Water-quality guideline after the processing can reach and surpass the service water standard, thoroughly realizes zero release, and does not produce secondary pollution.Because adopting this technology is to begin to handle (before the ammonia still process or after the ammonia still process waste water) from wastewater sources, and the water after handling will produce huge environmental benefit near surface water requirement to protection drinking water source water quality.
Compare with other process, adopt supercritical water oxidation technical finesse coking chemical waste water or organic waste water, structure of reactor is simple, volume is little, treatment capacity is big, applied widely, system carries out totally closed operation, non-secondary pollution, and the water after the processing can be used as the reuse water standard, be comparatively ideal coking chemical waste water or organic wastewater treatment process process, have good economy and environmental benefit.
The supercritical water oxidation method has wide application market and good promotion prospect because of the advantage of its high efficiency that has and economy and two aspects of environment.If supercritical water oxidation technical finesse coking chemical waste water or organic waste water technology can realize industrial experiment, and practiced on a large scale, not only the processing to China's coking industry waste water is a field technology revolution, and because supercritical water can realize to the separating of organic dissolving and inorganics that by the red-tape operati condition difficult organic and inorganic waste water that discharges for industries such as papermaking, plating, oil refining and municipal wastewater are handled all to be had and can be applied.
Description of drawings
Fig. 1 is the schema of supercritical water oxidation technical finesse coking chemical waste water of the present invention or organic waste water technology.
Reference numeral lists as follows:
1-coking chemical waste water or organic waste water, 2-ramp type efficient sedimentation tank, 3-flocculation agent chemicals dosing plant, 4-hydrolysis bucket, 5-Scale inhibitors chemicals dosing plant, 6-chemical tank or storage tank (Scale inhibitors), 7-plunger tpe force (forcing) pump, the 8-first-class heat exchanger, 9-well heater (super critical boiler), 10-desalination plant, 11-reactor, 12-secondary heat exchanger (oxygenant well heater), the 13-oxygenant adds pump, 14-oxygenant storage tank, 15-water cooler (band UTILIZATION OF VESIDUAL HEAT IN), the 16-regulator, 17-gas-liquid separator (band exhaust and water cycle are used).
Embodiment
The present invention will be described below in conjunction with accompanying drawing (Fig. 1).
Supercritical water oxidation technical finesse coking chemical waste water of the present invention or organic waste water technology, be to adopt supercritical water oxidation technical finesse coking chemical waste water or organic waste water, organic pollutant and oxygenant in the waste water all are dissolved in the water, oxidizing reaction is carried out in homogeneous phase, in the very short reaction times, the organic pollutant quilt is oxygenolysis rapidly, and utilizes the salt in the insoluble characteristic removal of the overcritical inorganics water.The present invention includes the pre-processing device of coking chemical waste water or organic waste water, remove solid particulate in the waste water with efficient inclined-plate clarifying basin, being transported to energy-saving interchanger with high-pressure pump then heats, be heated to 400 ℃ with super critical boiler during beginning, enter the demineralization plant desalination, the oxygenant that enters tubular reaction vessel and process heating and pressurizing then fully reacts, because reacting, this is autothermal reaction, temperature can be raised to 600 ℃, enter energy-saving interchanger again as thermal medium and the coking chemical waste water or the organic waste water heat exchange of newly coming in, reach the purpose of cooling and heating; And then enter the secondary heat exchanger heated oxidant; Be cooled to normal temperature from entering water cooler after secondary heat exchanger comes out, reclaim used heat, reconcile pressure, enter gas-liquid separator again and carry out gas-liquid separation with variable valve by water cooler, gaseous emission, water cycle is used.System has utilized the two-stage interchanger, and after system was stable, making full use of oxidation operation was the characteristic of autothermal reaction, no longer expends fuel in process of production, and can be with UTILIZATION OF VESIDUAL HEAT IN.Be provided with demineralization plant in the system, can remove the dissolved solids in the water, improve water quality.
So that this technology has is energy-conservation, water-saving, the organic nuisance of processing characteristics completely.
Fig. 1 is the schema of supercritical water oxidation technical finesse coking chemical waste water of the present invention or organic waste water technology.As shown in Figure 1, coking chemical waste water or organic waste water 1 enter the efficient ramp type settling tank 2 removal solid particulates that design has flocculation agent chemicals dosing plant 3, add antiseptic corrosion inhibitor (Scale inhibitors is stored in the chemical tank 6) by Scale inhibitors chemicals dosing plant 5 in the water outlet, enter piston high-pressure pump 7 again and be pressurized to 25MPa, be transported to energy-saving first-class heat exchanger 8 and carry out heat exchange with reacted hot water, original state, enter well heater (super critical boiler) 9 again and be heated to 400 ℃, can between 380-450 ℃, select other temperature, after system's operation, if temperature can reach 400 ℃ then do not entering super critical boiler 9, but directly enter desalination plant 10 desalinations, enter special substance then, the tubular reaction vessel 11 of special structure form and 12 heating of process secondary heat exchanger, the oxygenant of oxygenant force (forcing) pump 13 pressurizations fully reacts, because reacting, this is autothermal reaction, temperature can be raised to 600 ℃, enter energy-saving first-class heat exchanger 8 again as thermal medium and the coking chemical waste water or the organic waste water heat exchange of newly coming in, reach the purpose of cooling and heating; And then enter secondary heat exchanger 12 heated oxidants; Be cooled to normal temperature from entering water cooler 15 after secondary heat exchanger 12 comes out, and reclaim used heat, reconcile pressure, enter gas-liquid separator 17 again and carry out gas-liquid separation with regulator 16, gaseous emission, liquid circulation is used.Its characteristics are:
1, coking chemical waste water or organic waste water are in supercritical state (Tc 〉=374.3 ℃, Pc 〉=22.1MPa) following and oxygenant thorough mixing reaction, utilize the density of water under the supercritical state, viscosity, specific inductivity, the reduction of ionic product, hydrogen bond network structure between water molecules disappears, the specific inductivity of water is reduced to organic solvent approximate, the solubleness of organism in water significantly increases and micro-molecular gas, as hydrogen, oxygen, methane, carbonic acid gas etc. can arbitrary proportion and the miscible character of supercritical water, greatly reduce resistance to mass transfer, make organism in the several seconds, almost completely be oxidized to CO
2, H
2O and N
2, and can utilize under the supercritical state, the characteristic that inorganic salt are not allowed is removed the salinity in anhydrating, and the fine reuse water is provided.
2, system has utilized the two-stage interchanger, and after system was stable, making full use of oxidation operation was the characteristic of autothermal reaction, no longer expends fuel in process of production, and can be with UTILIZATION OF VESIDUAL HEAT IN.
3, adopted the inclined-plate clarifying basin that has the water inlet of chemicals dosing plant, bottom efficiently pre-processing device as coking chemical waste water or organic waste water.
4, in inclined-plate clarifying basin, drop into flocculation agent and improve sedimentation effect.
5, the corrosion inhibiting and descaling agent that added high temperature high voltage resistant before high-pressure pump reduces or stops fouling, the etching problem of heat-exchange equipment.
6, the structure formation of high-pressure pump, material, sealing all are fit to highly compressed and satisfy coking chemical waste water or organic waste water requires.
7, energy-saving interchanger adopts special structural design, uses special substance, has heat exchanger effectiveness height, little, corrosion-resistant, high temperature resistant, the high voltage bearing characteristics of resistance.
8, be provided with demineralization plant among the present invention, utilized water under supercritical state,, salt is separated out with the insoluble characteristic of inorganics.Outlet at demineralization plant is provided with filtering net and water flushing device, has not only prevented the obstruction of salt pair pipeline and reactor, has also realized the recycling of inorganic salt.
9, reactor adopts tubular reactor, and is simple in structure, adopts novel nickel based super alloy corrosion resistant material, has high pressure resistant, high temperature resistant, corrosion resistant characteristics.
10, water cooler adopts the energy-saving structure form, can reclaim used heat.
Have following characteristics in the process implementing of the present invention:
Supercritical water oxidation method is used for coking chemical waste water or organic waste water as a kind of advanced oxidation waste water, waste treatment technique, compares with other coking chemical waste water or organic wastewater treatment process, has following obvious superiority:
1, processing efficiency is high and thorough, and the processing rate of hazardous and noxious substances reaches more than 99.99%.
2, speed of reaction is fast, and the residence time is short, and mean residence time is less than 30s.
3, structure of reactor is succinct, and volume is little, and floor space is little.
4, do not produce secondary pollution, and removed the salt in the water, the waste water after the processing can be recycled fully, has saved the resource and the energy.
5, if processed waste water in organic concentration 1%～2%, just can rely on the heat that produces in the oxidation reaction process to keep the required heat energy of reaction, not need extraneous heat supplied, if Pollutant levels are higher, reaction can be emitted the more heat of oxidation, and these heat energy can return
Receive again and utilize.
Consider from economy that 6, supercritical water oxidation method processing of waste operating maintenance takes lower, the processed in units cost is lower, has wide industrial application values.
The technique effect that enforcement obtains:
1, technical process is simplified: at present treating coking wastewater biologicallies or the organic waste waters of adopting of coal chemical enterprise, exploitation successively and perfect " A-O, A more
2-O, A-O
2Etc. technology, mainly based on activated sludge process, this process complex procedures, floor space are big, investment cost is also higher, and the investment of general coking chemical waste water or organic waste water denitrogenation is ten thousand yuan of/ton water of 15-20, takes up an area of to be 100-150m
2/ ton water.Adopt supercritical water oxidation technical finesse coking chemical waste water or organic waste water, flow process is simple, because speed of response is fast, so volume of equipment is little, floor space is little, takes up an area of to be 10-15m
2/ ton water.
2, save water, cut down the consumption of energy: organic matter decomposition rate can reach 99.99%, and salt also can remove 95%, so water can reclaim fully, has reduced the consumption of water; Organic oxidizing reaction is an autothermal reaction, when concentration reaches 2%, need not heat basically, can also reclaim a part of used heat, has saved the energy.
3, protection environment:
Realize steady running in the successive wastewater treatment equipment, every pollutant emission indexs such as COD, ammonia nitrogen, colourity are well below discharging standards (GB 8978-96) in processing back coking chemical waste water or the organic waste water water outlet.See the following form:
| Title | Supercritical water oxidation technical finesse result | The GB8978-1996 first discharge standard |
| Volatile phenol (mg/L) | 0.126 | 0.5 |
| COD(mg/L) | 8.28 | 100 |
| SCN-(mg/L) | 0.021 | 0.5 |
| Ammonia-state nitrogen (mg/L) | 10.5 | 15 |
| Colourity | Water white transparency | 50 times |
| PH | 7 | 6-9 |
| Total salt/(g/L) | 0.37 | No requirement (NR) |
4, floor space is little: under supercritical state, resistance to mass transfer is little, is swift in response, and equipment volume is little, so floor space is little, and 1/10th of not enough biochemical process.
5, system is stable: not influenced by envrionment temperature etc., system is stable, stable effluent quality.
6, with wet oxidation process, burning method contrast:
| Parameter and index | Supercritical water oxidation | Wet oxidation | Burning method |
| Temperature/℃ | 400-650 | 150-350 | 1200-2000 |
| Pressure/Mpa | 25-30 | 2-20 | Normal pressure |
| Catalyzer | Can not add | Need | Do not need |
| The residence time/min | ≤0.5 | 15-20 | ≥10 |
| Clearance/% | ≥99.99 | 75-90 | ≥99 |
| Self-heating | Be | Be | Be not |
| Suitability | Pervasive | Restricted | Pervasive |
| Ejecta | Nontoxic, colourless | Poisonous, coloured | Dioxins, NOX etc. |
| Subsequent disposal | Do not need | Need | Need |
| Working cost/unit/m 3Waste water | ≤40 | ≤40 | 1600-2000 |
| / ten thousand yuan/m of investment 3Waste water | ≥100 | ≤80 | ≥200 |
Should be pointed out that the above embodiment can make those skilled in the art more fully understand the present invention, but do not limit the present invention in any way.Therefore, although this specification sheets has been described in detail the present invention with reference to drawings and Examples,, it will be appreciated by those skilled in the art that still and can make amendment or be equal to replacement the present invention; And all do not break away from the technical scheme and the improvement thereof of the spirit and scope of the present invention, and it all should be encompassed in the middle of the protection domain of patent of the present invention.
Claims (10)
1. supercritical water oxidation technical finesse coking chemical waste water or organic waste water technology is characterized in that comprising: coking chemical waste water or organic waste water are carried out pre-treatment, the waste water of the solid particulate that is removed; Waste water is by first-class heat exchanger or also by super critical boiler, enters desalination plant after being heated to 380-450 ℃, utilizes the insoluble characteristic of overcritical inorganics to remove salt in the waste water; Waste water behind the desalination is sent into reactor and the oxygenant generation autothermal reaction that passes through heating and pressurizing, obtain the higher High Temperature Gas water mixture of temperature; The High Temperature Gas water mixture enters first-class heat exchanger and is cooled to normal temperature as entering water cooler by secondary heat exchanger after thermal medium and the coking chemical waste water of newly coming in or the organic waste water heat exchange, behind regulator conciliation pressure, enter gas-liquid separator again and carry out gas-liquid separation, water cycle after gaseous emission, liquid are promptly handled is used.
2. supercritical water oxidation technical finesse coking chemical waste water according to claim 1 or organic waste water technology is characterized in that: the oxygenant of described heating and pressurizing is meant, enters reactor after the oxygenant in the oxygenant storage tank is pumped into the secondary heat exchanger preheating.
3. supercritical water oxidation technical finesse coking chemical waste water according to claim 1 or organic waste water technology is characterized in that: described reactor adopts tubular reaction vessel.
4. supercritical water oxidation technical finesse coking chemical waste water according to claim 1 or organic waste water technology, it is characterized in that: the salt discharge outlet of described desalination plant is provided with filtering net and water flushing device, not only prevent the obstruction of salt pair pipeline and reactor, also realized the recycling of inorganic salt.
5. supercritical water oxidation technical finesse coking chemical waste water according to claim 1 or organic waste water technology is characterized in that: described water cooler adopts the structure formation that reclaims used heat.
6. supercritical water oxidation technical finesse coking chemical waste water according to claim 1 or organic waste water technology, it is characterized in that: described super critical boiler has just begun as primary heater, system's operation is afterwards as auxiliary heater, that is: after waste water is heated to 380-450 ℃ by first-class heat exchanger, directly enter desalination plant, no longer pass through super critical boiler.
7. supercritical water oxidation technical finesse coking chemical waste water according to claim 1 or organic waste water technology is characterized in that: the ramp type settling tank is adopted in described pre-treatment, and adds flocculation agent to improve sedimentation effect in the ramp type settling tank.
8. supercritical water oxidation technical finesse coking chemical waste water according to claim 3 or organic waste water technology is characterized in that: described tubular reaction vessel adopts the nickel based super alloy corrosion resistant material.
9. supercritical water oxidation technical finesse coking chemical waste water according to claim 1 or organic waste water technology is characterized in that: the described waste water of removing solid particulate pumps into first-class heat exchanger by the plunger tpe force (forcing) pump.
10. supercritical water oxidation technical finesse coking chemical waste water according to claim 1 or organic waste water technology is characterized in that: add corrosion inhibiting and descaling agent in the described waste water of removing solid particulate, with fouling, the corrosion that reduces or stop heat-exchange equipment.
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