CN106807185A - A kind of wet method fume gas desulfurizing method - Google Patents
A kind of wet method fume gas desulfurizing method Download PDFInfo
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- CN106807185A CN106807185A CN201510845770.0A CN201510845770A CN106807185A CN 106807185 A CN106807185 A CN 106807185A CN 201510845770 A CN201510845770 A CN 201510845770A CN 106807185 A CN106807185 A CN 106807185A
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- alkaline residue
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- flue gas
- organic acid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/80—Semi-solid phase processes, i.e. by using slurries
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/606—Carbonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/70—Organic acids
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- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
Abstract
The present invention relates to a kind of wet method fume gas desulfurizing method, it is characterised in that：It is by the industrial wastewater containing acylate or organic acid, in waste residue addition lime wet type gas fume desulphurization system, it is less for containing organic acid and contain the more industrial wastewater of other organic matters, can increase in wherein adding flue gas desulphurization system after the content of organic acid by wet air oxidation.On the one hand the inventive method can improve flue gas desulphuization rate and improve lime utilization rate, while fully utilizing the valuable components in industrial wastewater, waste residue, not produce secondary pollution, reach the purpose of the treatment of wastes with processes of wastes against one another.The inventive method can be used for the flue gas desulfurization course of all kinds sulfur-containing oxide.
Description
1st, technical field
It is more particularly to a kind of to make full use of the useless of oil plant, chemical plant etc. the present invention relates to a kind of wet method fume gas desulfurizing method
The method that water carries out flue gas desulfurization.
2nd, background technology
Oxysulfide is a kind of gaseous contaminant that quantity is larger, influence face is wider in atmosphere pollution, mostly come from coal and
The combustion process of oil, and sulfide ore roasting, smelting process, wherein various boilers particularly power plant boiler smoke evacuation
With sulfoxide concentration it is low, exhaust gas volumn is big, floating dust is more the features such as and be difficult to administer.Flue gas desulfurization technique can be with the prior art
Be divided into dry desulfurization and wet desulphurization, because the desulfurization degree of wet desulfurizing process is high, technology maturation and in the industry using most,
Wherein it is most widely used with wet type lime method.The advantage of lime method is raw sorbent low cost, and subject matter is to inhale
The solubility for receiving agent is small, and utilization rate is low, and waste residue amount is big, during especially with cheap lime stone for absorbent, the problem
It is more prominent.
For the low problem of wet type lime method alkaline matter utilization rate, some solutions are proposed in the prior art, it is main
If addition has the auxiliary agent of cushioning effect in systems.As US5630991 proposes to be taken off in the flue gas with lime stone as absorbent
The ammonium ion of 500~7500ppm is added in sulphur system to improve the rate of dissolution of lime stone, therefore is reducing serum recycle amount
And there is desulfurization degree higher in the case of less calcium sulfur ratio.Addition organic acid is used for flue gas wet type lime as buffer
（Stone）Desulphurization system, oneself writes in eight textbooks as typical technology.
In petroleum refining process, refined product is washed with sodium hydroxide solution can discharge alkaline residue, according to refining
Oil product difference, alkaline residue can be further divided into often top gasoline alkaline residue, normal line alkaline residue, normal two wires alkaline residue, atmosphere 3rd side cut alkaline residue, urge
Change gasoline alkaline residue, catalytic diesel oil alkaline residue, coker gasoline alkaline residue, coker gas oil alkaline residue, liquid hydrocarbon alkali residue etc..These alkaline residues, mainly
It is made up of free alkali, neutral oil, sodium naphthenate, phenol sodium, sulfide, low molecular organic acidses salt etc., wherein sodium naphthenate mainly divides
In normal line alkaline residue, normal two wires alkaline residue, atmosphere 3rd side cut alkaline residue, phenol sodium is mainly distributed on often top gasoline alkaline residue and catalytic gasoline alkali to cloth
In slag, catalytic diesel oil alkaline residue, coker gasoline alkaline residue, coker gas oil alkaline residue, sulfide then concentrates on often top gasoline alkaline residue, catalysis vapour
In oily alkaline residue, coker gasoline alkaline residue, coker gas oil alkaline residue, catalytic diesel oil alkaline residue and liquid hydrocarbon alkali residue, low molecular organic acidses salt master
It is distributed in often top gasoline alkaline residue, normal line alkaline residue, normal two wires alkaline residue etc..Knowable to these alkaline residue compositions, if not to it
Deal carefully with, it will produce serious environmental pollution.
Existing alkaline residue treatment technology mainly has sulfuric acid neutralisation and carbon dioxide neutralisation.The alkaline residue for reclaiming aphthenic acids is neutralized
Process needs sulfuric acid to be acidified, and the water of generation is commonly referred to acid water, because its pH value is relatively low, and contains more organic contamination
Thing, such as low molecular organic acidses, belong to the sewage that harm is larger, treatment is more difficult.
Generally using plus alkali in and discharge, or the method discharged again after solvent extraction is processed.Carbon dioxide neutralisation is produced
Carbodiimide solution in containing the sodium carbonate more than school, difference in carbodiimide solution according to handled alkaline residue and usually contain the sulphur of different content
Compound, at the same also contain more organic matter, such as low molecular organic acidses, have the organic matter of certain solubility, do not separate thoroughly
Emulsion etc., its COD value can generally achieve 10000 more than mg/l.The processing method of alkaline residue carbodiimide solution is mainly and uses drying
Tower reclaims sodium carbonate therein, but because cost recovery is high, price is low economically " unable to make ends meet ", simultaneously because drying tail
Gas is seriously polluted and produces secondary pollution.Also having directly carry out alkaline residue wet oxidation to remove sulfide therein and part or complete
Portion COD is to reach discharge standard or the pretreatment as other treatment such as biochemical treatment, but exhaustive oxidation technique has condition severe
The shortcomings of quarter, equipment investment and operating cost high, although being relaxed as the wet-type oxidation technology condition of pretreatment, need into one
Step treatment, long flow path, investment and operating cost be not also low, meanwhile, both approaches all do not utilize having in alkaline residue carbodiimide solution
Value material, it may be said that be a kind of waste of resource.
3rd, the content of the invention
It is an object of the invention to provide a kind of operating cost is low, the treatment of wastes with processes of wastes against one another, make full use of it is various valuable in industrial wastewater
The fume desulphurization method of composition.
A kind of wet method fume gas desulfurizing method, adds in desulphurization system and contains organic acid soln, it is characterised in that the organic acid
Solution comes from industrial wastewater.
Described industrial wastewater be oil refinery alkaline residue, the sulfuric acid of oil refinery alkaline residue in and acid water, oil refinery alkali
With carbodiimide solution, paper mill alkaline sewage and containing the composite waste in organic acid wastewater in the carbon dioxide of slag.
Described oil refinery alkaline residue first passes through wet oxidation, then carries out pre-contact with flue gas, adds after isolating organic phase
In entering flue gas desulphurization system.
In the carbon dioxide of described oil refinery alkaline residue and carbodiimide solution first with flue gas carry out pre-contact, isolate organic phase
Afterwards in addition flue gas desulphurization system.
After first carrying out wet oxidation with carbodiimide solution in the carbon dioxide of described oil refinery alkaline residue, flue gas desulfurization is added
In system.
Described wet oxidation conditions are：Oxidizing temperature is 120~250 DEG C, and pressure is the pressure for keeping water to be liquid phase, oxygen
The change time is 20 minutes~2 hours, and oxidant is air, oxygen-enriched air or oxygen-enriched industrial waste gas, and contained amount of oxygen is by industry
Waste water exhaustive oxidation is 0.5~5 times of oxygen amount for needed for carbon dioxide.
Content of the described organic acid in desulfurization absorbs slurries is 0.5~5mmol/mol calcium.
Because principle of the invention is the treatment of wastes with processes of wastes against one another, so the ratio in industrial wastewater or waste residue addition absorbent can not
Make strict limitation.When exhaust gas volumn is smaller and when waste water or larger waste residue amount, the ratio of waste water or waste residue and lime or lime stone can
With big；When exhaust gas volumn is larger and when waste water or less waste residue amount, it is possible to reduce the addition of waste water or waste residue.But in order to reach
Preferable buffering effect, the content for absorbing organic acid in slurries is preferably 0.5~4mmol/mol calcium, organic in slurries are absorbed
When acid content reaches above range, absorbent preferably uses cheapest lime stone.
Flue gas desulfurization skill condition is essentially identical with the flue gas desulfurization condition of addition organic acid in the prior art, but in order to reach
Different purposes can suitably adjust operating condition.Such as calcium sulfur ratio be can suitably increase in order to improve desulfurization degree, internal circulating load, increasing increased
Plus gas residence time etc., but increase calcium sulfur ratio can make absorbent utilization rate low, increase internal circulating load and increase gas residence time
Equipment scale can be made huge, operating cost also correspondingly increases；Such as in order to improve absorbent utilization rate, calcium sulfur ratio can be reduced,
But desulfurization degree is impacted.During practical application, can be designed as needed.
The present invention carries out limewash method flue gas desulfurization according to the principle of the treatment of wastes with processes of wastes against one another with industrial wastewater, waste residue as additive,
On the one hand improve flue gas desulphuization rate improves absorbent utilization rate, reduces operating cost, reduces waste residue yield；The opposing party
Face solves the process problem of waste water, and various valuable components are utilized in making waste water.Can be widely applied to various types of
The flue gas desulfurization course of type, is particularly useful to produce in the flue gas desulfurization course of boiler in above-mentioned waste water, waste residue factory.
4th, specific embodiment
The solution of the present invention and effect are further illustrated with reference to embodiment, wherein COD value is chromium method.
Embodiment 1
The refined alkaline residue carbodiimide solution of oil plant catalytic gasoline, COD 30000mg/L;The mg/L of phenol 12000;PH value is 8.5.Wet type liquid
Phase oxidation condition：130 DEG C of oxidizing reaction temperature, reaction pressure 2.8MPa, void tower residence time of the spent lye in oxidation reactor
1.2h, air capacity is 3 times of exhaustive oxidation requirement.Organic acid content is 0.5 mol/l, predominantly low point in alkaline residue after oxidation
Sub- organic acid such 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
In the limestone pulping of limestone wet flue gas desulfurization, agstone is 200 mesh.Organic acid content is 2 in loop slurry
Mmol/mol calcium, solids content is 10%, and pH value is 5.0, and total calcium sulfur ratio is 1.1, and liquid-gas ratio is 7 l/rri3 flue gases, and gas-liquid connects
Touch（Hollow-spraying-tower）Time is 7 seconds.Desulfurization degree is 90%, and limestone utilization is 90%.
Embodiment 2
In the refined alkaline residue sulfuric acid of oil plant normal, two wires and acid water, COD 9483mg/L;Phenol 102mg/L;PH value is 3.2.
Acid water is used for limestone wet flue gas desulfurization slurrying, and agstone is 325 mesh.Organic acid content is 0.5 in loop slurry
Mmol/mol calcium, solids content is 15%, and pH value is 5.0, and total calcium sulfur ratio is 1.2, and liquid-gas ratio is 6 l/1T13 flue gases, and gas-liquid connects
The time of touching is 7 seconds, and desulfurization degree is 95%, and limestone utilization is 85%.
Embodiment 3
The refined mixing alkaline residue of Refinery Oil, the mg/L of COD 492880;The mg/L of phenol 1663;PH value is 12.The alkaline residue and flue gas
Contact carries out the pre- desulfurization of flue gas, and alkaline residue discharge carries out static layering when pH value reaches 4, and organic layer goes to reclaim and purifies, and water layer is direct
For lime slurrying.Organic acid content is 0.5mmol/mol calcium in loop slurry, and solids content is 12%, and pH value is 5.6, total calcium
Sulphur ratio is 1.0, and liquid-gas ratio is 7l/m3Flue 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, 220 DEG C of oxidizing reaction temperature, reaction pressure 4.5MPa, and spent lye is in oxygen
Change the void tower residence time 0.3h of reactor, air capacity is 0.8 times of exhaustive oxidation requirement.The pH value of alkaline residue is after oxidation
13.2, acylate content is that the 7.9 mol/lo alkaline residues carry out the pre- desulfurization of flue gas, alkaline residue when pH value reaches 4 with smoke contacts
Discharge carries out static layering, and organic layer goes purification, and water layer is directly used in limestone pulping, and agstone is 325 mesh.Loop slurry
Middle 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 6 1/H
I3 flue gases, gas-liquid contact（Hollow-spraying-tower）Time is 7 seconds, and desulfurization degree is 93%, and limestone utilization is 90%.
Claims (7)
1. a kind of wet method fume gas desulfurizing method, adds in desulphurization system and contains organic acid soln, it is characterised in that the organic acid is molten
Liquid comes from industrial wastewater.
2. according to the wet method fume gas desulfurizing method described in claim 1, it is characterised in that described industrial wastewater is oil refinery
In alkaline residue, the sulfuric acid of oil refinery alkaline residue and in acid water, the carbon dioxide of oil refinery alkaline residue and carbodiimide solution, paper mill alkalescence
Sewage and containing the composite waste in organic acid wastewater.
3. according to the wet method fume gas desulfurizing method described in claim 1, it is characterised in that described oil refinery alkaline residue is first passed through
Wet oxidation, then carry out pre-contact with flue gas, isolating in add after organic phase flue gas desulphurization system.
4. according to the wet method fume gas desulfurizing method described in claim 1, it is characterised in that the dioxy of described oil refinery alkaline residue
Change in carbon and carbodiimide solution first carries out pre-contact with flue gas, isolate after organic phase in addition flue gas desulphurization system.
5. according to the wet method fume gas desulfurizing method described in claim 1, it is characterised in that the dioxy of described oil refinery alkaline residue
Change in carbon and after carbodiimide solution first carries out wet oxidation, in adding flue gas desulphurization system.
6. according to the wet method fume gas desulfurizing method described in claim 1, it is characterised in that described wet oxidation conditions are：Oxidation
Temperature is 120~250 DEG C, and pressure is the pressure for keeping water to be liquid phase, and oxidization time is 20 minutes~2 hours, and oxidant is sky
Gas, oxygen-enriched air or oxygen-enriched industrial waste gas, contained amount of oxygen for by industrial wastewater exhaustive oxidation for needed for carbon dioxide oxygen amount
0.5~5 times.
7. in accordance with the method for claim 1, it is characterised in that described organic acid desulfurization absorb slurries in content be
0.5~5mmol/mol calcium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510845770.0A CN106807185A (en) | 2015-11-30 | 2015-11-30 | A kind of wet method fume gas desulfurizing method |
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| CN201510845770.0A CN106807185A (en) | 2015-11-30 | 2015-11-30 | A kind of wet method fume gas desulfurizing method |
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| CN106807185A true CN106807185A (en) | 2017-06-09 |
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Application publication date: 20170609 |