CN106348371B - The minimizing technology of volatile organic matter in a kind of water difficult to degrade - Google Patents

The minimizing technology of volatile organic matter in a kind of water difficult to degrade Download PDF

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Publication number
CN106348371B
CN106348371B CN201611011861.5A CN201611011861A CN106348371B CN 106348371 B CN106348371 B CN 106348371B CN 201611011861 A CN201611011861 A CN 201611011861A CN 106348371 B CN106348371 B CN 106348371B
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heat storage
superheated steam
organic matter
group
heat
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CN106348371A (en
Inventor
苏继新
王路瑶
程倩
程一倩
张晓霞
王国庆
潘齐
冯承湖
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Shandong Puxu Fuzhong Energy Saving And Environmental Protection Technology Co ltd
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Shandong University
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/02Treatment of water, waste water, or sewage by heating
    • C02F1/04Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/048Purification of waste water by evaporation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F22STEAM GENERATION
    • F22GSUPERHEATING OF STEAM
    • F22G1/00Steam superheating characterised by heating method
    • F22G1/14Steam superheating characterised by heating method using heat generated by chemical reactions
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23GCREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/04Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste liquors, e.g. sulfite liquors
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23GCREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2206/00Waste heat recuperation
    • F23G2206/20Waste heat recuperation using the heat in association with another installation
    • F23G2206/203Waste heat recuperation using the heat in association with another installation with a power/heat generating installation
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23GCREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2209/00Specific waste
    • F23G2209/10Liquid waste
    • F23G2209/101Waste liquor
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E20/00Combustion technologies with mitigation potential
    • Y02E20/12Heat utilisation in combustion or incineration of waste

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  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Heat Treatment Of Water, Waste Water Or Sewage (AREA)

Abstract

The minimizing technology of volatile organic matter in a kind of water difficult to degrade, waste water enters evaporator, the mixed vapour containing volatile organic matter that waste water evaporation generates enters heat storage by vapour compression machine, heat storage is at least provided with three groups, burning unit is first entered by first group of heat storage, it burns unit and on the one hand heats the organic matter burned in steam, on the one hand make heat storage accumulation of heat, mixed vapour becomes superheated steam after incinerating volatile organic matter, superheated steam returns to evaporator by second group of heat storage, heat is provided for evaporator, pass through superheated steam remaining mixed vapour purging intracorporal to third group accumulation of heat simultaneously;Then so that mixed vapour is sequentially entered next heat storage again, and next one heat storage is purged;This method supplements quantitative oxygen in high-temperature region, completes the complete oxidation of organic matter, flexible operation, organic matter removal is thorough, has achieved the purpose that energy-saving while combining waste water evaporation and high-temperature heat accumulation.

Description

The minimizing technology of volatile organic matter in a kind of water difficult to degrade
Technical field
The present invention relates to a kind of methods for removing volatile organic matter in water difficult to degrade, belong to sewage disposal technology neck Domain.
Background technique
The waste water of processing difficult to degrade is more, more typical such as garbage leachate, coking wastewater, chemical industry, medicine production Waste water etc..Hardly degraded organic substance is also many kinds of in water, and water quality is complicated, the complexity such as with high salt, peculiar smell, high-content volatile organism Situation proposes challenge to common biodegradable technique.
The processing of used water difficult to degradate with high salt can also directly adopt the processing of wet process high-level oxidation technology, but related engineering practice is still It has not been reported.Though direct combustion degradation is feasible technological means, it is contemplated that the amount of waste water is big, the high latent heat of vaporization, highly energy-consuming, height The factors such as cost, case history are also quite rare.
Salt density variation is complicated in industrial wastewater, and organism kinds are various, and traditional waste water treatment process generally uses Biggish conditioning tank is homogenized the concentration of salt and organic matter in waste water, and using the net of the low organic concentration after biodegrade Change the water outlet of water Macrodilution conditioning tank, to meet microorganism own growth and degradation of organic substances needs.From existing a large amount of works Journey practice sees, such as coking, pharmacy, pesticide, chemical industry, the treatment effect of the even industry-specific typical waste water in garbage leachate portion are equal It is difficult to meet the requirement for the wastewater discharge standard being increasingly stringenter, is badly in need of new treatment process.
Part new technology starts to avoid the influence that high salinity grows microorganism in waste water, after preparatory desalination or processing The method of desalination obtains the waste water of less salt, so as to subsequent Biochemical method.But more economical reverse osmosis deaslination processing by The influence of the factors such as organic matter, too high in salinity, therefore Some Enterprises are forced to take the higher evaporative desalination technique of cost.No matter It is triple effect evaporation or MVR (mechanical compression re-evaporation) desalination system, the effect of the desalination of process is preferable, but there is volatility in water Machine object, especially water-soluble volatile organic matter can enter in condensed water with subsequent condensation, and the organic pollution of condensed water is special The problem of not being refractory organic pollution, still remains.
High temperature incineration is clearly the quickly and effectively method for removing organic matter, and especially RTO (thermal accumulating incinerator) is relatively wide The general removal for the organic matter in exhaust gas, by the evaporation process of the high-salt wastewater containing organic matter and RTO technology, it may be convenient to By the latent heat utilization of waste water evaporation process and the coupling optimization of high-temperature oxydation burning process, organic matter in high-salt wastewater is substantially reduced Processing cost.
However, traditional high-temp combustion removal process containing volatile organic compounds does not need the supplement of oxygen, and waste water The gaseous component of evaporation is mainly vapor, and pyroprocess itself can be only formed the thermal cracking of organic matter, and be converted primarily into CO And H2, the final process of organic matter cannot be completed.
Summary of the invention
The present invention proposes a kind of operation spirit for deficiency existing for volatile organic matter removal technology in existing water difficult to degrade The minimizing technology of volatile organic matter in water difficult to degrade living, at low cost, this method are steamed using the heat accumulating type of waste water volatilization process The method that water removal middle and high concentration volatile organic matter is removed in vapour burning, has achieved the purpose that energy-saving.
The minimizing technology of volatile organic matter in water difficult to degrade of the invention is:
Waste water enters evaporator, and the mixed vapour containing volatile organic matter that waste water evaporation generates enters heat storage, stores Hot body enters burning unit by first group of heat storage at least provided with three groups, first, and is heated using the accumulation of heat of first group of heat storage Mixed vapour burns the organic matter in unit heating burning steam, and mixed vapour is heated to be superheated steam, superheated steam warp The process for crossing second group of heat storage discharges the sensible heat of steam, heats second group of heat storage, returns evaporator thereafter, for evaporation Device provides heat, at the same time superheated steam remaining mixed vapour purging intracorporal to third group accumulation of heat;When superheated steam is The inlet temperature T1 (entering temperature when heat storage by burning unit) and outlet temperature T2 of two heat storages are (by heat storage heel row Temperature out) temperature difference when reaching 20 DEG C, switching mixed vapour enters burning unit by second group of heat storage, and superheated steam passes through It crosses third group heat storage and returns to evaporator, while passing through superheated steam remaining mixed vapour purging intracorporal to first group of accumulation of heat; When superheated steam third group heat storage outlet temperature T2 and the mixed vapour inlet temperature T1 temperature difference reach 20 DEG C when, switching is mixed It closes steam and burning unit is entered by third group heat storage, superheated steam returns to evaporator by first group of heat storage, leads to simultaneously Cross superheated steam remaining mixed vapour purging intracorporal to second group of accumulation of heat;When superheated steam is in first group of heat storage and outlet temperature T2 and when reaching 20 DEG C of inlet temperature T1 are spent, so that mixed vapour is passed through first group of heat storage again and enters burning unit;So follow Ring, until wastewater treatment finishes;
The condensed water generated in evaporator is discharged by base of evaporator, and remaining fixed gas can be discharged by evaporator tail end, is steamed Send out the concentration salt of waste water remaining after evaporation or the discharge port discharge that salt water is concentrated by evaporator in device.
Incineration temperature T in the burning unit is set as 700-850 DEG C.
It burns required air in unit to be provided by the air pipe line connecting with burning unit, air capacity is discharged by heat storage The oxygen content of superheated steam determines that oxygen content percent by volume is 0.5-1%.
The present invention supplements quantitative oxygen in high-temperature region while combining waste water evaporation and high-temperature heat accumulation, completes organic The saturated vapor of the complete oxidation of object, waste water evaporation process becomes superheated steam during regenerative oxidation, and in subsequent evaporation The hot fluid side of device unit discharges heat, and the fixed gas in exhaust gas is then handled by subsequent blow valve emptying, completes high-salt wastewater The evaporation of middle volatile organic matter, burning disposal process.Flexible operation, organic matter removal is thorough, has reached energy-saving mesh 's.
Detailed description of the invention
Fig. 1 is the principle schematic diagram of the removal system of volatile organic matter in water difficult to degrade in the present invention.
In figure: 1. evaporators, 2. vacuum pumps, 3. vapour compression machines, 4. circulating fans, 5. oxygen content probe, 6. first store Hot body, 7. second heat storages, 8. third heat storages, 9. burn unit, 10. combustion gas inlet pipes, 11. air inlet lines, 12. mixed vapours Pipeline, 13. superheated steam pipelines, 14. scavenging pipelines;The first intake valve of 1A., the second intake valve of 1B., 1C. third intake valve, The first blow down valve of 2A., the second blow down valve of 2B., 2C. third blow down valve, the first air outlet valve of 3A., the second air outlet valve of 3B., 3C. third Air outlet valve.
Specific embodiment
The system for realizing the minimizing technology of volatile organic matter in present invention water difficult to degrade, as shown in Figure 1, including evaporator 1, the first heat storage 6, the second heat storage 7, third heat storage 8 and burning unit 9.Evaporator 1 is connect with superheated steam pipeline 13, The outlet of evaporator 1 is connected with mixed vapour pipeline 12, and scavenging pipeline 14 is connected on superheated steam pipeline 13.It can be steamed in mixing Vapour compression machine 3 (if vapour compression machine can not had to using triple effect evaporation system), scavenging pipeline 14 are connected on vapor pipeline 12 On be connected with circulating fan 4.Oxygen content probe 5 is connected on superheated steam pipeline 13.
First heat storage 6 by the first intake valve 1A, the first blow down valve 2A and the first air outlet valve 3A respectively with mixed vapour Pipeline 12, scavenging pipeline 14 and superheated steam pipeline 13 connect.Second heat storage 7 passes through the second intake valve 1B, the second blow down valve 2B and the second air outlet valve 3B is connect with mixing vapor pipeline 12, scavenging pipeline 14 and superheated steam pipeline 13 respectively.Third stores Hot body 8 by third intake valve 1C, third blow down valve 2C and third air outlet valve 3C respectively with mix vapor pipeline 12, scavenging conduit Road 14 and superheated steam pipeline 13 connect.First heat storage 6, the second heat storage 7 and third heat storage 8 connect with burning unit 9 It connects, burns unit 9 and connect with combustion gas inlet pipe 10 and air inlet lines 11.
Usual waste water can be used for the next stage evaporator of triple effect evaporation process by the vapor of evaporator evaporation generation Heat source, or after entering vapour compression machine adiabatic heating in MVR system, for the conducting self-heating of waste water in evaporator, concentration Evaporator is discharged in salt or concentration salt water.It is that will introduce to burn unit 9 containing the mixed vapour of volatile organic matter in the present invention, After burning the organic matter in mixed vapour, evaporator 1 is come back to.
Details are provided below to volatile organic matter removal in water difficult to degrade for above system.
(1) waste water enters evaporator 1, and the mixed vapour containing volatile organic matter that waste water evaporation generates enters mixing and steams Vapor pipeline 12 enters heat storage by vapour compression machine 3 by mixed vapour pipeline 12, is entered by heat storage and burn unit 9, burned On the one hand unit 9 heats the organic matter burned in steam, on the one hand make heat storage accumulation of heat.It is organic that mixed vapour incinerates volatility Become oxygen-containing superheated steam after object, evaporator 1 is come back to by superheated steam pipeline 13, heat is provided for evaporator 1, for steaming The heating of waste water in device is sent out, the condensed water of generation is discharged by 1 bottom of evaporator, and remaining fixed gas can be passed through by 1 tail end of evaporator The discharge of 2 negative pressure of vacuum pump, or be discharged through positive pressure system by vent valve.
Waste water enters the concentration salt of 1 remaining after evaporation of evaporator or salt water is concentrated to be discharged by the discharge port of evaporator 1.
(2) mixed vapour enters before burning unit 9, measures the temperature T1 in scavenging pipeline 14.
Three valve alternate cycles that (3) three heat storages cooperate it to connect use, and complete burning and heat exchange.Single accumulation of heat Three valve groups on body can only open one in work, and other two is to close.In namely working, the first heat storage 6 On the first intake valve 1A, the first blow down valve 2A and tri- valves of the first air outlet valve 3A only one is open-minded;On second heat storage 7 The second intake valve 1B, the second blow down valve 2B and tri- valves of the second air outlet valve 3B only one is open-minded;On third heat storage 8 Only one is open-minded by third intake valve 1C, third blow down valve 2C and third air outlet valve 3C.
Mixed vapour enters the first heat storage 6 (the first blow down valve 2A and the first outlet at this time through the first intake valve 1A first Valve 3A is to close), 6 top of the first heat storage is heated and risen to through the first heat storage 6, into burning unit 9.Burn unit Temperature T in 9 is 700-850 DEG C, burns the organic matter in degradation mixed vapour in incineration area.Purified superheated steam, warp Second heat storage 7 and the second air outlet valve 3B leave burning unit 9, and (the second intake valve 1B and the second blow down valve 2B is to close at this time ), then cooling when superheated steam passes through the second heat storage 7 enters evaporator 1 by superheated steam pipeline 13.Meanwhile to third The remaining mixed vapour of heat storage 8 purges, and opens circulating fan 4, opens third blow down valve 2C, and circulating fan 4 passes through scavenging conduit Superheated steam clean in superheated steam pipeline 13 is delivered to third heat storage 8 by road 14, and 8 inner pore of stripping third heat storage is empty Interior mixed vapour containing organic matter;The mixed gas of generation, which enters, burns unit 9, with the mixing risen through the first heat storage 6 Organic matter burning process is completed in steam mixing.
When the temperature difference of steam (saturated vapor) inlet temperature T1 and outlet temperature T2 (passing through the temperature being discharged after heat storage) When reaching 20 DEG C (temperature difference of temperature T2 and saturated vapor T1 when namely superheated steam is by the second heat storage 7), make second Heat storage 7 is switched to mixed vapour and rises heating channel, that is, closes the first intake valve 1A, closes on the second heat storage 7 Second air outlet valve 3B opens the second intake valve 1B, and mixed vapour is made to heat and burn by the second heat storage 7.Purified mistake Hot steam is left through third heat storage 8 and third air outlet valve 3C and burns (the third intake valve 1C and third blow down valve 2C at this time of unit 9 It is to close), then cooling when superheated steam passes through third heat storage 8 enters evaporator 1 by superheated steam pipeline 13.Meanwhile To the remaining mixed vapour purging of the first heat storage 6, circulating fan 4 is opened, the first blow down valve 2A is opened, circulating fan 4 passes through Part superheated steam clean in superheated steam pipeline 13 is delivered to the first heat storage 6, the first accumulation of heat of stripping by scavenging pipeline 14 Mixed vapour containing organic matter in 6 inner pore space of body;The mixed gas of generation, which enters, burns unit 9, and through the second heat storage 8 Organic matter burning process is completed in the mixed vapour mixing of rising.
When superheated steam is when the temperature difference of the outlet temperature T2 and inlet temperature T1 of third heat storage 8 reach 20 DEG C, then make Third heat storage 8 is switched to mixed vapour and rises heating channel, that is, closes the second intake valve 1B, closes third heat storage 8 On third air outlet valve 3C, open third intake valve 1C, make mixed vapour by third heat storage 8 heat and burn.After purification Superheated steam again through the first heat storage 6 and the first air outlet valve 3A leave burn unit 9 (the first intake valve 1A and first is blown at this time Sweeping valve 2A is to close), then cooling when superheated steam passes through the first heat storage 6 enters evaporator by superheated steam pipeline 13 1.Meanwhile the remaining mixed vapour of the second heat storage 7 is purged, the second blow down valve 2B is opened, circulating fan 4 passes through scavenging pipeline The superheated steam of superheated steam pipeline 13 inner part cleaning is delivered to the second heat storage 7 by 14, and the mixed gas of generation, which enters, burns Unit 9 is burnt, is mixed with the mixed vapour risen through third heat storage 8 and completes organic matter burning process.
When superheated steam 6 outlet temperature T2 of the first heat storage and saturated vapor inlet temperature T1 and the temperature difference reach 20 DEG C When, then so that the first heat storage 6 is switched to mixed vapour and rise heating channel, that is, close third intake valve 1C, close first The first air outlet valve 3A on heat storage 6 opens the first intake valve 1A, and mixed vapour is made to heat and burn by the first heat storage 6.
In this way, by the following progress that moves in circles: mixed vapour enters the first heat storage 6-- and burns the burning degradation of unit 9 -- Superheated steam is discharged by the second heat storage 7 and is purged to third heat storage 8 -- and mixed vapour enters the second heat storage 7-- and burns list Member 9 burns degradation -- superheated steam is discharged by third heat storage 8 and is purged to the first heat storage 6 -- mixed vapour and enters third storage Hot body 8- burns the burning degradation-superheated steam of unit 9 and is discharged by the first heat storage 6 and is purged to the second heat storage 7.
The unlatching logical relation of each control valve is determined by solenoid valve logic controller.
It burns the required oxygen that burns in unit 9 to be provided by the air inlet lines 11 at 9 top of burning unit, burn in unit 9 When 700-850 DEG C of section of setting is not achieved in temperature T, from combustion gas inlet pipe 10 and air inlet lines 11 to top burner additional heat To set temperature.Required air quantity is by being arranged on superheated steam pipeline 13 for measuring the superheated steam being discharged by heat storage 6 Oxygen content probe 5 measurement after determine, oxygen content percent by volume be 0.5-1%.

Claims (3)

1. the minimizing technology of volatile organic matter in a kind of water difficult to degrade, it is characterized in that:
Waste water enters evaporator, and the mixed vapour containing volatile organic matter that waste water evaporation generates enters heat storage, heat storage Three groups are provided with, burning unit is first entered by first group of heat storage, unit is burned and on the one hand heats the organic matter burned in steam, On the one hand become superheated steam after so that heat storage accumulation of heat, mixed vapour is incinerated volatile organic matter, superheated steam passes through second Group heat storage returns to evaporator, provides heat for evaporator, while intracorporal to third group accumulation of heat remaining mixed by superheated steam Close steam blowing;When the temperature difference of the superheated steam in the outlet temperature T2 and saturated vapor inlet temperature T1 of the second heat storage reaches 20 DEG C when, make to mix saturated vapor burning unit entered by second group of heat storage, superheated steam passes through third group heat storage and returns to Evaporator, while passing through superheated steam remaining mixed vapour purging intracorporal to first group of accumulation of heat;When superheated steam is in third group When the temperature difference of the outlet temperature T2 and inlet temperature T1 of heat storage reach 20 DEG C, enter mixed vapour by third group heat storage Unit is burned, superheated steam returns to evaporator by first group of heat storage, while by superheated steam in second group of heat storage Remaining mixed vapour purging;When superheated steam reaches in the outlet temperature T2 and the temperature difference of inlet temperature T1 of first group of heat storage At 20 DEG C, so that mixed vapour is passed through first group of heat storage again and enter burning unit;So circulation, until wastewater treatment finishes.
2. the minimizing technology of volatile organic matter in water difficult to degrade according to claim 1, it is characterized in that: the burning is single Incineration temperature T in member is set as 700-850 DEG C.
3. the minimizing technology of volatile organic matter in water difficult to degrade according to claim 1, it is characterized in that: burning in unit Required air is provided by the air pipe line connecting with burning unit, and air capacity is true by the oxygen content for the superheated steam that heat storage is discharged Fixed, oxygen content percent by volume is 0.5-1%.
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