CN105435608A - Wet flue gas desulfurization method - Google Patents
Wet flue gas desulfurization method Download PDFInfo
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- CN105435608A CN105435608A CN201410497451.0A CN201410497451A CN105435608A CN 105435608 A CN105435608 A CN 105435608A CN 201410497451 A CN201410497451 A CN 201410497451A CN 105435608 A CN105435608 A CN 105435608A
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Abstract
The invention relates to a wet flue gas desulfurization method, and is characterized in that industrial wastewater and waste residues containing organic acid salts or organic acids are added to a lime wet flue gas desulfurization system, and the industrial wastewater containing fewer organic acids but containing more other organic matters can be oxidized by wet air to increase the content of the organic acids and then is added to the flue gas desulfurization system. The method can improve the flue gas desulphurization rate and improve lime utilization rate, besides, comprehensively utilizes valuable components in the industrial wastewater and the waste residues, does not produce secondary pollution, thereby achieving the purpose of using waste to treat waste. The method can be used in the desulfurization process of various types of sulfur oxide-containing flue gases.
Description
Technical field
The present invention relates to a kind of wet method fume gas desulfurizing method, particularly relate to a kind of method that waste water making full use of oil plant, chemical plant etc. carries out flue gas desulfurization.
Background technology
Oxysulfide is a kind of gaseous contaminant that in atmosphere pollution, quantity is comparatively large, influence surface is wider, mainly come from the combustion process of coal and oil, and the roasting of sulfide ore, smelting process, wherein various boiler particularly power plant boiler smoke evacuation there is the features such as sulfoxide concentration is low, exhaust gas volumn is large, floating dust is many and be difficult to administer.In prior art, flue gas desulfurization technique can be divided into dry desulfurization and wet desulphurization, because the desulfurization degree of wet desulfurizing process is high, technology maturation and apply at most in the industry, is wherein most widely used with wet type lime method.The advantage of lime method is that raw sorbent cost is low, and subject matter is that the solubility of absorbent is little, and utilization rate is low, and waste residue amount is large, and when particularly adopting low-cost lime stone to be absorbent, this problem is more outstanding.
For the problem that wet type lime method alkaline matter utilization rate is low, in prior art, propose some solutions, mainly add the auxiliary agent with cushioning effect in systems in which.As US5630991 proposes the ammonium ion adding 500 ~ 7500ppm in the flue gas desulphurization system taking lime stone as absorbent, improving the rate of dissolution of lime stone, therefore when reducing serum recycle amount and less calcium sulfur ratio, there is higher desulfurization degree.Add organic acid and be used for flue gas wet type lime (stone) desulphurization system as buffer, oneself writes in eight textbooks as typical technology.
In petroleum refining process, alkaline residue can be discharged with sodium hydroxide solution detergent preparing petroleum products, according to the difference of refined oil product, alkaline residue can be further divided into and often push up gasoline alkaline residue, a normal line alkaline residue, normal two wires alkaline residue, atmosphere 3rd side cut alkaline residue, FCC gasoline caustic sludge, catalytic diesel oil alkaline residue, coker gasoline alkaline residue, coker gas oil alkaline residue, liquid hydrocarbon alkali residue etc.These alkaline residues, primarily of free alkali, neutral oil, sodium naphthenate, phenol sodium, sulfide, the compositions such as low molecular organic acids salt, wherein sodium naphthenate is mainly distributed in a normal line alkaline residue, normal two wires alkaline residue, in atmosphere 3rd side cut alkaline residue, phenol sodium is mainly distributed in normal top gasoline alkaline residue and FCC gasoline caustic sludge, catalytic diesel oil alkaline residue, coker gasoline alkaline residue, in coker gas oil alkaline residue, sulfide then concentrates on and often pushes up gasoline alkaline residue, FCC gasoline caustic sludge, coker gasoline alkaline residue, coker gas oil alkaline residue, in catalytic diesel oil alkaline residue and liquid hydrocarbon alkali residue, low molecular organic acids salt is mainly distributed in and often pushes up gasoline alkaline residue, a normal line alkaline residue, in normal two wires alkaline residue etc.From these alkaline residue compositions, if do not dealt carefully with them, serious environmental pollution will be produced.
Existing alkaline residue treatment technology mainly contains sulfuric acid neutralisation and carbon dioxide neutralisation.The alkaline residue N-process reclaiming aphthenic acids needs sulfuric acid acidation, and the water of generation is commonly referred to acid water, because its pH value is lower, and containing more organic pollution, as low molecular organic acids etc., belongs to the sewage that harm is comparatively large, process is more difficult.
Usual employing adds in alkali and discharge, or the method for discharging again after solvent extraction process.Containing the sodium carbonate that school is many in the carbodiimide solution that carbon dioxide neutralisation produces, sulfide according to the difference of handled alkaline residue usually containing different content in carbodiimide solution, simultaneously also containing more organic matter, as low molecular organic acids, have the organic matter of certain solubility, be not separated emulsion etc. thoroughly, its COD value can reach more than 10000mg/l usually.The processing method of alkaline residue carbodiimide solution is mainly and adopts drying tower recovery sodium carbonate wherein, but because cost recovery is high, price is low economically " unable to make ends meet ", produces secondary pollution because dried tail gas is seriously polluted simultaneously.Also have alkaline residue directly carried out wet oxidation remove sulfide wherein and partly or entirely COD using reach discharge standard or as other process as the pretreatment of biochemical treatment, but exhaustive oxidation technique has the shortcomings such as condition harshness, equipment investment and operating cost are high, although relax as pretreated wet-type oxidation technology condition, but need process further, long flow path, investment and operating cost also not low, simultaneously, these two kinds of methods all do not utilize the valuable substance in alkaline residue carbodiimide solution, can be described as a kind of waste of resource.
Summary of the invention
The object of the present invention is to provide that a kind of operating cost is low, the treatment of wastes with processes of wastes against one another, make full use of the fume desulphurization method of various valuable components in industrial wastewater.
A kind of wet method fume gas desulfurizing method, adds containing organic acid soln, it is characterized in that this organic acid soln comes from industrial wastewater in desulphurization system.
Described industrial wastewater is in the sulfuric acid of oil refinery alkaline residue, oil refinery alkaline residue and acid water, oil refinery alkaline residue carbon dioxide in and carbodiimide solution, paper mill alkaline sewage and containing the composite waste in organic acid wastewater.
Described oil refinery alkaline residue first through wet oxidation, then carries out pre-contact with flue gas, adds in flue gas desulphurization system after isolating organic phase.
First carry out pre-contact with flue gas with carbodiimide solution in the carbon dioxide of described oil refinery alkaline residue, add in flue gas desulphurization system after isolating organic phase.
After first carrying out wet oxidation with carbodiimide solution in the carbon dioxide of described oil refinery alkaline residue, then add in flue gas desulphurization system.
Described wet oxidation conditions is: oxidizing temperature is 120 ~ 250 DEG C, pressure is keep water to be the pressure of liquid phase, oxidization time is 20 minutes ~ 2 hours, oxidant is air, oxygen-enriched air or oxygen enrichment industrial waste gas, and contained amount of oxygen is for by industrial wastewater exhaustive oxidation 0.5 ~ 5 times of oxygen amount needed for carbon dioxide.
The content that described organic acid absorbs in slurries in desulfurization is 0.5 ~ 5mmol/mol calcium.
Because principle of the present invention is the treatment of wastes with processes of wastes against one another, so the ratio that industrial wastewater or waste residue add in absorbent can not do strict restriction.When the less and waste water of exhaust gas volumn or waste residue amount larger time, the ratio of waste water or waste residue and lime or lime stone can be more greatly; When the comparatively large and waste water of exhaust gas volumn or waste residue amount less time, the addition of waste water or waste residue can be reduced.But in order to reach good buffering effect, absorb organic acid content in slurries and be preferably 0.5 ~ 4mmol/mol calcium, when in absorption slurries, organic acid content reaches above-mentioned scope, absorbent preferably adopts cheapest lime stone.
Flue gas desulfurization skill condition with to add organic acid flue gas desulfurization condition in prior art substantially identical, but suitably can adjust operating condition to reach different objects.As can be suitably increased calcium sulfur ratio to improve desulfurization degree, adding big cycle volume, increasing gas residence time etc., but increasing calcium sulfur ratio can make absorbent utilization rate low, adding big cycle volume and increasing gas residence time to make equipment scale huge, and operating cost also correspondingly increases; As in order to improve absorbent utilization rate, calcium sulfur ratio can be reduced, but desulfurization degree is influenced.During practical application, can design as required.
The present invention, according to the principle of the treatment of wastes with processes of wastes against one another, carries out limewash method flue gas desulfurization with industrial wastewater, waste residue for additive, improves flue gas desulphuization rate on the one hand. and improve absorbent utilization rate, reduce operating cost, reduce waste residue output; Solve the process problem of waste water on the other hand, make various valuable components in waste water all obtain utilization.Various types of flue gas desulfurization course can be widely used in, be specially adapted to produce in the flue gas desulfurization course of boiler in above-mentioned waste water, waste residue factory.
Detailed description of the invention
Further illustrate the solution of the present invention and effect below in conjunction with embodiment, wherein COD value is chromium method.
Embodiment 1
Oil plant catalytic gasoline refines alkaline residue carbodiimide solution, COD30000mg/L; Phenol 12000mg/L; PH value is 8.5.Wet type liquid phase oxidation condition: oxidizing reaction temperature 130 DEG C, reaction pressure 2.8MPa, spent lye is at the void tower time of staying 1.2h of oxidation reactor, and air capacity is 3 times of exhaustive oxidation requirement.After oxidation, in alkaline residue, organic acid content is 0.5mol/l, is mainly low molecular organic acids as formic acid, acetic acid, propionic acid, butyric acid, 3 Methylbutanoic acid, 2 monomethyl valeric acids, caproic acid etc.Carbodiimide solution after oxidation is used for the limestone pulping of limestone wet flue gas desulfurization, and agstone is 200 orders.In loop slurry, organic acid content is 2mmol/mol calcium, and solids content is 10%, and pH value is 5.0, and total calcium sulfur ratio is 1.1, and liquid-gas ratio is 7l/rri3 flue gas, and gas-liquid contact (hollow-spraying-tower) time is 7 seconds.Desulfurization degree is 90%, and limestone utilization is 90%.
Embodiment 2
Oil plant is normal one, two wires is refined in alkaline residue sulfuric acid and acid water, COD9483mg/L; Phenol 102mg/L; PH value is 3.2.Acid water is used for limestone wet flue gas desulfurization slurrying, and agstone is 325 orders.In loop slurry, organic acid content is 0.5mmol/mol calcium, and solids content is 15%, and pH value is 5.0, and total calcium sulfur ratio is 1.2, and liquid-gas ratio is 6l/1T13 flue gas, and gas-liquid contact time is 7 seconds, and desulfurization degree is 95%, and limestone utilization is 85%.
Embodiment 3
Refinery Oil refining mixing alkaline residue, COD492880mg/L; Phenol 1663mg/L; PH value is 12.This alkaline residue and smoke contacts carry out the pre-desulfurization of flue gas, and when pH value reaches 4, alkaline residue is discharged and carried out static layering, and organic layer goes to reclaim and purifies, and water layer is directly used in lime slurrying.In loop slurry, organic acid content is 0.5mmol/mol calcium, and solids content is 12%, and pH value is 5.6, and total calcium sulfur ratio is 1.0, and liquid-gas ratio is 7l/m
3flue gas, gas-liquid contact time is 6 seconds, and desulfurization degree is 92%, and lime utilization rate is 92%.
Embodiment 4
Alkaline residue in embodiment 3, carries out wet oxidation, oxidizing reaction temperature 220 DEG C, reaction pressure 4.5MPa, and spent lye is at the void tower time of staying 0.3h of oxidation reactor, and air capacity is 0.8 times of exhaustive oxidation requirement.After oxidation, the pH value of alkaline residue is 13.2, acylate content is that this alkaline residue of 7.9mol/lo and smoke contacts carry out the pre-desulfurization of flue gas, and when pH value reaches 4, alkaline residue is discharged and carried out static layering, and organic layer goes to purify, water layer is directly used in limestone pulping, and agstone is 325 orders.In loop slurry, organic acid content is 3mmol/mol calcium, and solids content is 10%, and pH value is 5.6, and total calcium sulfur ratio is 1.0, and liquid-gas ratio is 61/Hi3 flue gas, and gas-liquid contact (hollow-spraying-tower) time is 7 seconds, and desulfurization degree is 93%, and limestone utilization is 90%.
Claims (7)
1. a wet method fume gas desulfurizing method, adds containing organic acid soln in desulphurization system, it is characterized in that this organic acid soln comes from industrial wastewater.
2. according to wet method fume gas desulfurizing method according to claim 1, it is characterized in that described industrial wastewater be in the sulfuric acid of oil refinery alkaline residue, oil refinery alkaline residue and acid water, oil refinery alkaline residue carbon dioxide in and carbodiimide solution, paper mill alkaline sewage and containing the composite waste in organic acid wastewater.
3., according to wet method fume gas desulfurizing method according to claim 1, it is characterized in that described oil refinery alkaline residue is first through wet oxidation, then carry out pre-contact with flue gas, add in flue gas desulphurization system after isolating organic phase.
4., according to wet method fume gas desulfurizing method according to claim 1, it is characterized in that first carrying out pre-contact with flue gas with carbodiimide solution in the carbon dioxide of described oil refinery alkaline residue, add in flue gas desulphurization system after isolating organic phase.
5., according to wet method fume gas desulfurizing method according to claim 1, after it is characterized in that first carrying out wet oxidation with carbodiimide solution in the carbon dioxide of described oil refinery alkaline residue, then add in flue gas desulphurization system.
6. according to wet method fume gas desulfurizing method according to claim 1, it is characterized in that described wet oxidation conditions is: oxidizing temperature is 120 ~ 250 DEG C, pressure is keep water to be the pressure of liquid phase, oxidization time is 20 minutes ~ 2 hours, oxidant is air, oxygen-enriched air or oxygen enrichment industrial waste gas, and contained amount of oxygen is for by industrial wastewater exhaustive oxidation 0.5 ~ 5 times of oxygen amount needed for carbon dioxide.
7. in accordance with the method for claim 1, it is characterized in that the content that described organic acid absorbs in slurries in desulfurization is 0.5 ~ 5mmol/mol calcium.
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| CN201410497451.0A CN105435608A (en) | 2014-09-26 | 2014-09-26 | Wet flue gas desulfurization method |
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