CN101920159A - Method for removing and reclaiming sulfur dioxide from gas by low power consumption renewable absorbent - Google Patents
Method for removing and reclaiming sulfur dioxide from gas by low power consumption renewable absorbent Download PDFInfo
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- CN101920159A CN101920159A CN 201010278086 CN201010278086A CN101920159A CN 101920159 A CN101920159 A CN 101920159A CN 201010278086 CN201010278086 CN 201010278086 CN 201010278086 A CN201010278086 A CN 201010278086A CN 101920159 A CN101920159 A CN 101920159A
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Abstract
The invention relates to a method for removing and reclaiming sulfur dioxide from a mixed gas by a renewable absorbent, which is characterized by comprising the following steps: adopting an absorbent to contact with a gas containing sulfur dioxide, and removing the sulfur dioxide in the gas, wherein the absorbent comprises the components as follows by mass concentration: 10-30% of inorganic base and/or complex salt thereof and/or sulfite thereof, 0.02-0.2% of antioxidant and water; after absorbing the sulfur dioxide, reacting a solution containing the sulfur dioxide with another organic amine absorbent, and transferring the sulfur dioxide in the organic amine absorbent, thereby obtaining a renewable absorbent for removing the sulfur dioxide in air current repeatedly, wherein the organic amine absorbent comprises the following components by mass concentration: 30-98% of organic amine, 0.0-0.2% of antioxidant and water; and desorbing the organic amine absorbent containing the sulfur dioxide to obtain a high concentration sulfur dioxide gas and a renewable organic amine absorbent. The method for absorbing and reclaiming the sulfur dioxide proposed by the invention can realize cycled regeneration and utilization of the absorbent, and has no secondary pollution in the use process, low power consumption and low operation cost.
Description
Technical field
The present invention relates to a kind of employing Regeneratable absorbent and from mist, remove and reclaim sulfur dioxide (SO
2) method.
Background technology
SO
2Be China's atmosphere pollution major pollutants, annual discharge capacity is more than 2,000 ten thousand tons, and its main source is a large amount of low concentration SO that the field produced such as metallurgy, thermoelectricity, thermoelectricity and chemical industry
2Flue gas is therefore to SO in the flue gas
2Improvement is to reduce SO
2The major measure of polluting.
In existing sulfur removal technology, utilize SO in the direct absorbing and removing flue gas of absorbent
2Be one of most effectual way,, mainly be divided into following two classes according to present used absorbent difference:
One class is inorganic alkaline process, comprising: based on the calcium method of lime, lime stone, based on the magnesium method of magnesia, based on the sodium method of sodium carbonate, with NH
3Be the ammonia process on basis etc.In order to last method, though can remove SO in the flue gas
2, but in use, used inorganic base generally all needs earlier through hydration process, and desulfurization product need carry out oxidation processes for reaching discharge standard, causes problems such as equipment investment is big, operation and maintenance cost height; The while absorbent can not be realized recycling, causes a large amount of wastings of resources, and the desulfurization product added value is low, and is general directly discarded, easily causes secondary pollution problems.
Propose to adopt in (CN1481926A) as domestic patent " a kind of flue gas desulfurization by magnesia wet method and product reclaim new technology " and in the absorption tower, propose underflow, generate magnesium sulfate technology through oxidation, do not relate to improvement, cause the secondary pollution of the wasting of resources and accessory substance flue gas desulfurization absorption and regeneration of absorption solution technology.And patent " sulfur removal technology of using external regenerative cycle magnesium sulfate method flue gas or waste gas " (CN101607173A) in, utilize magnesia and magnesium bisulfite to obtain magnesium sulfite and carry out flue gas desulfurization by outer loop regeneration, but the method still needs constantly to replenish magnesia, the magnesium bisulfite amount of Sheng Chenging can get more and more simultaneously, fail really to realize recycling absorbent, and end product also has to abandon as solid waste, has the wasting of resources and secondary pollution problem equally.
Another kind of is organic alkaline process, utilizes organic amine and salt thereof to be absorbent usually, removes the SO in the flue gas
2, this method is representative with Canadian Cansolv company employing technology.But because organic amine costs an arm and a leg, so adopt this method investment bigger, organic amine is to SO simultaneously
2The mole number that absorbs is bigger, though absorbent can be recycling, needs to consume a large amount of steam, general 1 ton of SO
2Steam consumption quantity greater than 10 tons.The organic amine absorbent is absorbing SO in addition
2In, directly contacting with gaseous mixture, gas is discharged can take away the part organic amine simultaneously, causes the organic amine loss; Oxygen in the gas and organic amine salt reaction simultaneously generates heat stable salt, because the existence of heat stable salt has reduced absorbent to SO
2Assimilation effect, cause organic amine consumption problem in use.
And absorption SO provided by the invention
2Method combines the advantage of existing desulfur technology, has avoided that absorbent can't be recycling in the inorganic base, causes the wasting of resources and desulfurization product pollution problem, saves the aquation and the desulfurization product oxidizing process of inorganic base in the former technology, has reduced equipment investment; Remedied in organic alkaline process the big problem of energy consumption in the organic amine consumption and absorbent cyclic process simultaneously.The absorbent that this method is used, absorbability is big, and energy consumption is low, and absorbent is stable and can be recycling and can reclaim high concentration SO
2Gas does not produce solid waste, and cost of investment is low, has better solved existing SO
2Remove the shortcoming of technology.
Summary of the invention
The invention provides a kind of absorbent medium of utilizing from containing SO
2Absorb SO in the gas
2, and the method that absorbent regeneration is recycled, this method key step is:
(1) makes and contain SO
2Mist contact with absorbent A, from this mist, absorb SO
2, formation meets SO
2The gas of emission concentration standard and solution B.
Wherein, absorbent A contains inorganic base and/or its double salt and/or sulphite and antioxidant.
Inorganic base meets molecular formula M (OH) among the absorbent A
x, wherein M is a metallic element, x is the valence state of M.Described inorganic base can generate solubility or microsolubility sulphite, bisulfites.Wherein said alkali is, for example Mg (OH)
2, Al (OH)
3, Mn (OH)
2, Zn (OH)
2, Cu (OH)
2, Fe (OH)
2, Fe (OH)
3Deng; Double salt is mainly the sulfate and the sulfurous acid of above inorganic base, for example: alkali formula magnesium sulfite, alkali magnesium sulfate, alkali formula zinc sulfite, alkali formula aluminium sulfite etc.; Because in the step (2), subsulfate can be produced stable organic amine sulfate with organic amine, so the double salt composition is preferably the alkali acid sulphite hereinafter; Sulphite is mainly the sulphite of contained metallic element in the above inorganic base, for example: MgSO
3, Zn SO
3, Cu SO
3, Al
2(SO
3)
3The above various inorganic base, its double salt and sulphite only for for example, are not limited only to above content but contained inorganic base, its double salt and sulphite comprise.
Contained inorganic base, its double salt and sulphite can be single components in the prescription, also can be the combinations of two or more composition.
The antioxidant that contains among the absorbent A is aromatic amine, phenols, quinones, alcohols, ethers and derivative thereof, or sulphur and thiosulfate; Aromatic amine such as diphenylamines, p-phenylenediamine (PPD), EEDQ etc.; Phenols such as hydroquinones etc.; Quinones as: 2, the 6-tert-butyl group-4-methylphenol anthraquinone, 2-methylanthraquinone etc.; Alcohols is as ethanol, two 12 carbon alcohol esters, two ten four carbon alcohols esters and two octadecanol esters etc.; Ethers such as MEHQ, two (3, three grades of butyl of 5--4-hydroxy phenyl) thioether glycol ether etc.; Thiosulfate is as sodium thiosulfate, magnesium thiosulfate etc.; Be preferably benzenediol, 2-methylanthraquinone, MEHQ, thiosulfate etc.Its effect is to prevent that absorbent from absorbing SO
2After the sulphite and the bisulfites that obtain be stable sulfate by the dioxygen oxidation in the gas, hinder the regeneration of absorbent.The above various antioxidant only for for example, is not limited only to above content but contained antioxidant comprises.
Contained antioxidant can be single component in the prescription, also can be the combination of two or more antioxidant.
In absorbent A, also can contain organic amine, described organic amine is in hereinafter the step (2), when obtaining absorbent regeneration A, to remain in the organic amine among the absorbent regeneration A.
Also contain water among the absorbent A.
Particularly, absorbent A contains: the inorganic base of 10%～30% quality, its double salt and sulphite or both and both above mixtures; 0.0 the antioxidant of～0.2% quality; The solvent of absorbent A is a water; Each component sum is 100 quality %.
Step (1) is preferably carried out under 10～70 ℃ of temperature, is 20～60 ℃ more preferably, most preferably is 30～50 ℃.
In the step (1), absorbent and SO
2Mass ratio be that 200～500g absorbent absorbs 100g SO
2Quality, be preferably 200～400g absorbent and absorb 100g SO
2Quality.
Absorbent A absorbs the SO in the gas
2After, generate and contain SO
2Solution B, along with SO in the solution B
2The increase of content, the pH value can decrease, for increasing SO in the solution B
2Content, generating B solution final pH value is between 2.0～4.0.
SO
2Emission concentration standard is the corresponding discharge standard of every profession and trade that meets the provisions of the relevant regulations issued by the State.
Main component in the solution B is that contained inorganic base among the absorbent A, its double salt and sulphite absorb SO
2After the sulfate mixture that obtains of the sulphite, bisulfites and the oxidation thereof that are converted into, wherein be main component with the bisulfites.The mechanism reaction equation is as follows:
SO
2+H
2O→H
2SO
3
M(SO
3)
x/2+x/4O
2→M(SO
4)
x/2
M(HSO
3)
x+x/2O
2→M(SO
4)
x/2+x/2H
2SO
4
yM(SO
3)
x/2·M(OH)
x+x/2SO
2→(y+1)M(SO
3)
x/2+x/2H
2O
(2) make solution B and absorbent C hybrid reaction in reactor after the absorption, make the pH of mixed value be controlled at 4.0～9.0, be preferably 5.0～7.5, SO
2From solution B, separate, transfer among the absorbent C, pass through separating, washing, obtain solid insoluble and solution D, the solid insoluble composition is the mixture of inorganic base, its double salt and sulphite among the former absorbent A, according to inorganic base, its double salt and sulfite concentration among the former absorbent A, be mixed with absorbent regeneration A with water in proportion.The main component of solution D is the SO in contained organic amine and the solution among the absorbent C
2The sulfurous acid and the bisulfites of the organic amine that reaction generates.
The reaction temperature of step (2) is 20～70 ℃, is preferably 30～60 ℃, most preferably is 45～50 ℃.
Organic amine is example with the primary amine, and concrete reaction mechanism is as follows:
After solution B and the absorbent C reaction, the SO in the solution B more than 40～70%
2Transfer among the absorbent C.
Absorbent C contains: the organic amine of 30%～98% quality is preferably the organic amine of 35～85% quality; 0.0～0.2% mass reactance oxidant is preferably 0.05～0.15% mass reactance oxidant; The solvent of absorbent C is a water; Each component sum is 100 quality %.
Among the absorbent C, organic amine can be fatty amine, aromatic amine, heterocyclic amine, comprises primary amine, secondary amine, tertiary amine and derivative separately thereof, and it can utilize SO in the alkalescence realization of organic amine and inorganic base and the double salt thereof
2Exchange.Particularly, in the described organic amine, fatty amine comprises: ethylenediamine, AEEA, N, N ', N '-(trimethyl)-N-(2-ethoxy)-ethylenediamine; N, N ', N ', N '-four (2-ethoxy)-ethylenediamine, N, N '-dimethyl-N, N '-two (2-ethoxy)-ethylenediamine, N, N ', N ', N '-four (2-ethoxy)-1, the 3-diaminopropanes, 4-methyl-diaminopropane, N, N-dimethylethanolamine, diethanol amine, triethanolamine, dicyandiamide, diethylenetriamine, triethylene tetramine, TEPA, polyethylene polyamine etc. and derivative thereof; Aromatic amine comprises as diazo aminobenzene, o ethyl aniline, m-phenylene diamine (MPD), N, N '-dimethylaniline, xylidine etc. and derivative thereof; Heterocyclic amine comprises as pyridine, 4-picoline, imidazoles, glyoxal ethyline, morpholine, quinoline, 1,4-diazabicylo [2.2.2] octane, piperazine, hydroxyethyl piperazine, aminoethyl piperazine, N, N '-lupetazin, N-(2-ethoxy) piperazine, N, two (2-ethoxy) piperazines of N-etc. and derivative thereof.Be preferably: 4-methyl-diaminopropane, triethylene tetramine, TEPA, diazo aminobenzene, N, N '-dimethylaniline, pyridine, imidazoles, 4-methylquinoline, piperazine, hydroxyethyl piperazine, N, N '-lupetazin, aminoethyl piperazine, N-(2-ethoxy) piperazine, N, or derivatives thereofs such as N '-two (2-ethoxy) piperazine.The above various organic amine only for for example, is not limited only to above content but contained organic amine comprises.
Contained organic amine can be single component among the absorbent C, also can be the combination of two or more organic amine.
The antioxidant that contains among the absorbent C is aromatic amine, phenols, quinones, alcohols, ethers and derivative thereof, or sulphur and thiosulfate; Aromatic amine is as diphenylamines, p-phenylenediamine (PPD), EEDQ etc.; Phenols is as hydroquinones etc.; Quinones as: 2, three grades of butyl of 6--4-methylphenol anthraquinone, 2-methylanthraquinone etc.; Alcohols is as ethanol, two 12 carbon alcohol esters, two ten four carbon alcohols esters and two octadecanol esters etc.; Ethers is as MEHQ, two (3, three grades of butyl of 5--4-hydroxy phenyl) thioether glycol ether etc.; Thiosulfate is as sodium thiosulfate, magnesium thiosulfate etc.; Be preferably: benzenediol, 2-methylanthraquinone, MEHQ, thiosulfate etc.Its effect is to prevent that absorbent from absorbing SO
2After the sulphite and the bisulfites that obtain be stable sulfate by the dioxygen oxidation in the gas, hinder the regeneration of absorbent.It can be identical or different with the used antioxidant of step (1).The above various antioxidant only for for example, is not limited only to above content but contained antioxidant comprises.
Contained antioxidant can be single component in the prescription, also can be the combination of two or more antioxidant.
In absorbent C, also can contain the organic amine complex compound, described organic amine complex compound is in hereinafter the step (3), when obtaining absorbent regeneration C, the complex compound that institute's metal ion generates among organic amine and the absorbent B.
(3) according to SO in organic amine and the solution among the absorbent C
2The decomposition temperature of the unstable salt that reaction generates is carried out desorb with the absorption liquid D that obtains in (2), with gaseous state SO in desorption apparatus
2From D solution, separate sucking-off, obtain high-purity SO
2Gas and absorbent regeneration C.
In the desorption process, can utilize steam stripping, or inert gas passes absorption liquid D stripping, or by thin film evaporator to the solution D desorb, or solution D is carried out desorb by methods such as atomization and vaporization desorbs, above method can also can be carried out under negative pressure at normal pressure, and the unstable salt in the solution is decomposed, and separates sucking-off SO
2Gas.During the desorb, amine salt returns to the form of its alkali, makes the SO that exists with sulphite and bisulfites in the solution
2As gaseous state SO
2From solution D, desorb.And the pH value of solution raises usually in desorption process, along with pH value in the solution D raises, and SO
2The difficulty of separating sucking-off also increases, and the pH value of the absorbent regeneration C that obtains after the desorb should be preferably 6.8～7.5 between 6.0～9.5, is to SO simultaneously when guaranteeing absorbent regeneration C and solution B reaction
2Absorbability, the SO that is contained among the absorbent regeneration C that requires to obtain
2Content is lower than below 20%.Simultaneously the content of the sta-salt that wherein generates through oxidation also should be controlled at below 2%.
Compared with prior art, adopt method of the present invention to absorb SO
2, to invest lowly, operating cost is low in the use, and energy consumption is low, non-secondary pollution.
Method of the present invention and MgO method relatively do not need the hydration process in early stage, and also aerobicization not of desulfurization product reduced equipment investment simultaneously, and in absorption process, single with Mg (OH)
2Be absorbent, but be absorbent with inorganic base and double salt thereof or two kinds of mixtures.In the method for the invention, inorganic base and double salt thereof or two kinds of mixtures absorb SO
2The back generates M (SO
3)
X/2And M (HSO
3)
x, M (SO
3)
X/2And M (HSO
3)
xBy react the M that obtains regenerating (OH) with organic amine
xAnd the double salt absorbent, directly circulation is used to absorb SO
2, realize the circular regeneration of absorbent, and during regeneration and the reaction temperature of organic amine be 20～70 ℃.And in the existing MgO technology, general with the MgSO that obtains
3Product is oxidized to MgSO
4, MgSO
4Added value is lower, and is general directly discarded, forms secondary pollution easily; Perhaps with MgSO
3And Mg (HSO
3)
2Heat to decompose more than 800 ℃ and obtain the MgO that regenerates, the realization absorbent regeneration.Compare with this method, the absorbent regeneration energy consumption is bigger, and when high temperature regeneration, part MgO meeting inactivation causes the absorbent loss.
Secondly, compare with the organic amine absorption techniques, existing organic amine absorption techniques utilizes the direct gaseous mixture contact of organic amine, absorbs gaseous state SO wherein
2In actual applications, owing to O in the gaseous mixture
2With the sulfite oxidation of organic amine is stable organic amine sulfate, thereby has reduced organic amine to SO
2Absorption efficiency, cause the loss of organic amine, and purified gas can take the part organic amine out of, also cause the organic amine loss, so in the running, expense is higher.And this method is to utilize organic amine and M (SO
3)
X/2And M (HSO
3)
xSO in the solution
2Reaction is with the SO in the solution
2Transfer in the organic amine, avoided directly contacting, then obtain high-purity SO by desorb again with gas
2With regeneration organic amine absorbent, whole process is a confined space, has reduced problems such as the oxidation of organic amine and loss.In desorption process, owing to can adopt multiple desorption mode, consume a large amount of steam, energy consumption problem of higher when having solved former method desorb.
Description of drawings
Accompanying drawing 1 process of desulfurizing gases simplified flow chart of the present invention
Specific embodiment
The present invention will be described below in conjunction with example, but its purpose is not a restriction range of application of the present invention.
Embodiment 1
A certain 2Ot/h chain furnace boiler exhaust gas, SO in the gas
2Content is 2000～5000ppm, and temperature is 150 ℃.From wherein drawing after part of smoke enters the absorption tower, through spray washing, remove wherein dust and SO earlier
3And cooling, enter absorber portion then, the SO in the flue gas
2Be absorbed agent A and absorb, gas is discharged from the top, absorption tower, absorbs SO
2The pH value of back solution B is 2.5～2.8, then enter in the reactor, add absorbent C to pH value 5.5～6.0,50 ℃ of reaction temperatures are then separated through washing, obtain sediment and solution D, sediment is the absorbent A of regeneration, and after the making beating of serum pump, it is recycling to enter the absorption tower with inorganic base and double salt concentration and water among the former absorbent A, solution D is introduced in the desorption apparatus, obtained SO through the steam desorb
2Gas and absorbent regeneration C are that 6.8～7.0 absorbent regeneration C enter the reactor cycles utilization with the pH value.
Absorbent slurry A composition is: the Mg of 20 quality % (OH)
2, 0.2 quality % magnesium thiosulfate, all the other are water;
Absorbent C composition is: 80 quality % TEPAs, and 0.2 quality % magnesium thiosulfate, all the other are water;
Its service data is as follows:
Embodiment 2
As condition among the embodiment 1, difference is:
Absorbent A composition is: 10 quality %Mg (OH)
2, 5 quality % alkali formula magnesium sulfites, 0.1 quality % sulphur, all the other are water;
Absorbent C composition is: 80 quality % TEPAs, and 0.2 quality % magnesium thiosulfate, all the other are water;
Its service data is as follows:
Embodiment 3
As condition among the embodiment 1, difference is:
Absorbent slurry A composition is: the Mg of 15 quality % (OH)
2, the MgSO of 5 quality %
3, 0.15 quality % p-phenylenediamine (PPD), all the other are water;
Absorbent C composition is: 50 quality % triethylene tetramines, and 10 quality % AEEAs, 0.1 quality % sulphur, all the other are water;
Its service data is as follows:
Embodiment 4
As condition among the embodiment 1, difference is:
Absorbent A composition is: 15 quality %Al (OH)
3, 0.1 quality % sulphur, 0.05 quality % ethanol, all the other are water for the two ten four carbon alcohols esters of 0.2 quality %;
Absorbent C composition is: 70 quality % triethylene tetramines, and 10 quality %N, N '-dimethylaniline, the two 12 carbon alcohol esters of 0.1 quality %, all the other are water;
Absorb SO
2The pH value of back solution B is 2.0～2.5;
Its service data is as follows:
Embodiment 5
As condition among the embodiment 1, difference is:
Absorbent A composition is: 12%Mn (OH)
2, 0.1 quality % hydroquinones, all the other are water;
Absorbent C composition is: 30 quality % o ethyl anilines, and 20 quality % m-phenylene diamine (MPD)s, 10 quality % xylidine, 0.1 quality % diphenylamines, all the other are water;
Its service data is as follows:
Embodiment 6
As condition among the embodiment 1, difference is:
Absorbent A composition is: 18%Zn (OH)
2, two (3, three grades of butyl of 5--4-hydroxy phenyl) the thioether glycol ethers of 0.1 quality %, all the other are water;
Absorbent C composition is: 20 quality %N, and N ', N ', N '-four (2-ethoxy)-1, the 3-diaminopropanes, 10 quality % dicyandiamides, 30 quality % 4-methyl-diaminopropanes, 0.1 quality %2-tectoquinone, all the other are water;
Solution D adopts low pressure atomization and vaporization method to carry out desorb, obtains SO after desorb
2Gas and absorbent regeneration C, absorbent regeneration C control pH value is 6.6～7.0, reproducibility absorbent C enters the reactor cycles utilization.
Its service data is as follows:
Embodiment 7
As condition among the embodiment 1, difference is:
Absorbent A composition is: 15%Zn (OH)
2, 5% alkali formula zinc sulfite, 0.1 quality %2-tectoquinone, all the other are water;
Absorbent C composition is: 35 quality % AEEAs, 15 quality %N, and N ', N '-(trimethyl)-N-(2-ethoxy)-ethylenediamine, 0.1 quality %2, three grades of butyl of 6--4-methylphenol anthraquinone, all the other are water;
Solution D adopts low pressure atomization and vaporization method to carry out desorb, obtains SO after desorb
2Gas and absorbent regeneration C, absorbent regeneration C control pH value is 6.6～7.0, reproducibility absorbent C enters the reactor cycles utilization.
Its service data is as follows:
Embodiment 8
A certain smeltery sinter fume, SO in the gas
2Content is 7000～13000ppm, and temperature is 50～60 ℃.After flue gas enters the absorption tower, the SO in the flue gas
2Be absorbed agent A slurries and absorb, gas is discharged from the top, absorption tower, absorbs SO
2The pH value of back solution B is 2.5～2.8, then absorbent B enters reactor, it is 6.0～6.5 that adding absorbent C is mixed to the pH value, separate through washing, obtaining sediment is reproducibility absorbent A, with 30% mass concentration and water after the serum pump is pulled an oar, it is recycling to enter the absorption tower, absorbent D is introduced in the thin film evaporator, carry out gas and carry, obtain SO
2Gas and reproducibility absorbent C, the pH value is 7.3～7.8 among the control reproducibility absorbent C, then reproducibility absorbent C enters the reactor cycles utilization.
Absorbent slurry A composition is: 30 quality % alkali formula magnesium sulfites, and 0.1 quality % sodium thiosulfate, 0.05% quality % sulphur, all the other are water;
Absorbent C composition is: 40 quality %N, and N '-two (2-ethoxy) piperazine, 20 quality % aminoethyl piperazines, 0.1 quality % sodium thiosulfate, 0.05% quality % sulphur, all the other are water;
Its service data is as follows:
Embodiment 9
As condition among the embodiment 8, difference is:
Absorbent A composition is: 15 quality %Mg (OH)
2, 5 quality % alkali formula magnesium sulfites, 0.1 quality % sodium thiosulfate, all the other are water;
Absorbent C composition is: 20 quality % hydroxyethyl piperazines, and 40 quality %N-(2-ethoxy) piperazine, 0.05 quality % EEDQ, all the other are water;
Its service data is as follows:
Embodiment 10
As condition among the embodiment 8, difference is:
Absorbent A composition is: 15 quality %Al (OH)
3, 5 quality % alkali formula aluminium sulfites, 0.1 quality % sodium thiosulfate, all the other are water;
Absorbent C composition is: 15 quality %1, and 4-diazabicylo [2.2.2] octane, 40 quality %N, N '-lupetazin, 5 quality %N, N-dimethylethanolamine, 0.1 quality % sodium thiosulfate, all the other are water;
Its service data is as follows:
Embodiment 11
As condition among the embodiment 8, difference is:
Absorbent A composition is: 15 quality %Zn (OH)
2, 5 quality %ZnSO
3, 0.1 quality % sodium thiosulfate, 0.05% quality % sulphur, all the other are water;
Absorbent C composition is: 10 quality % hydroxyethyl piperazines, and 40 quality %N-(2-ethoxy) piperazine,, 10 quality %4-picolines, 0.1 MEHQ, all the other are water;
Absorb SO
2The pH value of back solution B is 1.8～2.0, and then absorbent B enters reactor, and it is 6.0～65 that adding absorbent C is mixed to the pH value,
Solution D adopts passes through N
2Method is carried out gas and is proposed desorb, obtains SO after desorb
2Gas and absorbent regeneration C, absorbent regeneration C control pH value is 6.8～7.0, reproducibility absorbent C enters the reactor cycles utilization.
Its service data is as follows:
Embodiment 12
As condition among the embodiment 8, difference is:
Absorbent A composition is: 15 quality %Mg (OH)
2, 5 quality %Zn (OH)
2, 0.1 quality % sodium thiosulfate, 0.05% quality % sulphur, all the other are water;
Absorbent C composition is: 50 quality %N, and N '-two (2-ethoxy) piperazine, 5 quality %2-methylimidazoles, the two octadecanol esters of 0.1 quality %, the two 12 carbon alcohol esters of 0.05% quality %, all the other are water;
Absorb SO
2The pH value of back solution B is 2.0～2.5, and then absorbent B enters reactor, and it is 6.0～65 that adding absorbent C is mixed to the pH value,
Solution D adopts passes through N
2Method is carried out gas and is proposed desorb, obtains SO after desorb
2Gas and absorbent regeneration C, absorbent regeneration C control pH value is 6.8～7.0, reproducibility absorbent C enters the reactor cycles utilization.
Its service data is as follows:
Claims (14)
1. one kind is utilized absorbing medium from containing SO
2Absorb SO in the mist
2And make the method for absorbing medium circular regeneration by processing, this method comprises:
(1) makes and contain SO
2Mist contact with absorbent A, from this mist, absorb SO
2, formation meets SO
2The gas of emission concentration standard and solution B;
(2) solution B that obtains is mixed with absorbent C, make SO wherein
2From B, transfer among the absorbent C,, obtain insoluble matter and solution D by separating, washing;
(3), this absorbent regeneration A is circulated back to the SO that absorbs in (1) in the gas with the absorbent regeneration A that obtains after the insoluble matter that obtains in (2) and the water proportioning
2
(4) solution D that obtains in (2) is carried out desorb, collect SO
2Gas obtains absorbent regeneration C simultaneously;
(5) the absorbent regeneration C with step (4) is recycled to (2) step;
Wherein, described absorbent A contains inorganic base and/or its double salt and/or sulphite and antioxidant;
Described absorbent C contains organic amine and antioxidant.
2. the method described in claim 1, wherein the described inorganic base of absorbent A meets molecular formula: M (OH)
x, wherein M is a metallic element, x is the valence state of M.
3. method as claimed in claim 1 or 2, wherein the inorganic base among the absorbent A is Mg (OH)
2, Al (OH)
3, Mn (OH)
2, Zn (OH)
2, Cu (OH)
2, Fe (OH)
2And/or Fe (OH)
3Deng; Described double salt is the sulfate and the sulphite of described inorganic base; Described sulphite is the sulphite of contained metallic element in the described inorganic base.
4. method as claimed in claim 1 or 2, wherein the composition of absorbent A is: the inorganic base of 10%～30% quality, its double salt and sulphite or both and both above mixtures, 0.0 the antioxidant of～0.2% quality, and water, each component sum are 100 quality %.
5. as each described method in the claim 1～4, wherein, antioxidant is aromatic amine, phenols, quinones, alcohols, ethers and derivative thereof, sulphur or thiosulfate among the absorbent A.
6. method as claimed in claim 1 or 2, wherein the contained organic amine of absorbent C is fatty amine, aromatic amine or heterocyclic amine.
7. method as claimed in claim 1 or 2, wherein the contained organic amine of absorbent C is primary amine, secondary amine, tertiary amine or its derivative separately.
8. method as claimed in claim 1 or 2, wherein the contained organic amine of absorbent C is 4-methyl-diaminopropane, triethylene tetramine, TEPA, diazo aminobenzene, N, N '-dimethylaniline, pyridine, imidazoles, 4-methylquinoline, piperazine, hydroxyethyl piperazine, N, N '-lupetazin, aminoethyl piperazine, N-(2-ethoxy) piperazine, N, N '-two (2-ethoxy) piperazine or derivatives thereof.
9. method as claimed in claim 1 or 2, wherein absorbent C contains: the organic amine of 30%～98% mass concentration; 0.0～0.2% mass concentration antioxidant; The solvent of absorbent C is a water; Each component sum is 100 quality %.
10. method as claimed in claim 1 or 2, wherein identical or different among contained antioxidant of absorbent C and the absorbent A is aromatic amine, phenols, quinones, alcohols, ethers or derivatives thereof or sulphur or thiosulfate.
11. the method for claim 1, wherein the main component in the solution B is contained inorganic base or its double salt or both mixtures absorption SO among the absorbent A
2After the sulfate mixture that obtains of the sulphite, bisulfites and the oxidation thereof that are converted into.
12. the method for claim 1 is characterized in that: in step (2), the pH value of control mixed liquor is 4.0～9.0, is preferably 5.0～7.5.
13. the method for claim 1 is characterized in that: following method is adopted in the desorb in the step (4): steam stripping, inert gas pass absorption liquid D stripping, thin film evaporator desorb or atomization and vaporization desorb.
14. the method for claim 1 is characterized in that: the pH value that obtains absorbent regeneration C in the step (4) after the desorb is 5.0～9.5, is preferably 6.0～8.0.
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