CN101874981B - Method for regenerating desulfurizer - Google Patents
Method for regenerating desulfurizer Download PDFInfo
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- CN101874981B CN101874981B CN2009102254228A CN200910225422A CN101874981B CN 101874981 B CN101874981 B CN 101874981B CN 2009102254228 A CN2009102254228 A CN 2009102254228A CN 200910225422 A CN200910225422 A CN 200910225422A CN 101874981 B CN101874981 B CN 101874981B
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- anion exchange
- exchange resin
- desulfurizing agent
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- type anion
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Abstract
The invention provides a method for regenerating a desulfurizer, which comprises a step of making the desulfurizer prepared by contacting a sulfur dioxide-containing mixed gas contacted with an anion exchange resin, wherein the anion exchange resin is a weakly basic epoxy type anion exchange resin. By adopting the method for regenerating the desulfurizer, SO42-, C2O42- and Cl- in the desulfurizer can be removed effectively, so the heat stable salts in the desulfurizer are removed, and then the desulfurizer is regenerated.
Description
Technical field
The present invention relates to a kind of renovation process of desulfurizing agent, particularly relate to the method that removes of heat stable salt in a kind of flue gas desulfurization amine liquid.
Background technology
The aqueous solution of alkali compounds such as organic amine solution is widely used in sour gas (hydrogen sulfide, carbon dioxide, sulfur dioxide etc.) and removes and reclaim.Its principle is that the sour gas of low concentration contacts the organic amine salt that the back generation can be decomposed with alkali lye; Form rich solution; In desorber, carry out heating desorption then, the sour gas that discharges high concentration is recycled, and the amine liquid that obtains after the desorb simultaneously can reuse through after the Regeneration Treatment.
Oxygen content is very high in the sinter fume; The organic amine desulfuration solution exists the oxidative degradation of three kinds of degraded modes such as organic amine aqueous solution, the thermal degradation of organic amine solution and the chemical degradation of organic amine solution in to the process of sintering flue gas desulfurization; Organic amine can generate organic acids such as formate, acetate, oxalate through after the above-mentioned degraded; Yet, the corrosion of the existence meeting acceleration equipment of lot of organic acids radical ion, corrosion product carries out enrichment easily and causes that equipment stops up and change the character of sweetening liq; Cause a series of problems such as sweetening liq foaming, increased the maintenance of operating cost and equipment; And; Owing to contain a spot of hydrogen chloride, fluoride, hydrogen sulfide, nitrogen oxide, organic sulfur etc. in the flue gas; These materials with can generate corresponding acid group and sulphur simple substance after the organic amine desulfuration solution contacts, to understand partial oxidation be sulfate ion to the sulfite ion in the sweetening liq simultaneously; In addition; Above-mentioned organic anion, inorganic anion can combine with organic amine to generate can not desorb in desorber thermal-stable salt; When the content of thermal-stable salt reached certain amount, said sweetening liq began deterioration, and desulfurized effect can obviously descend.
Disclose a kind of renovation process of chain triacontanol amine solution of the heat stable salts that contains alkanolamine among the US5162084, contained highly acid anion and acidulous anion in the said chain triacontanol amine solution, said method comprises:
(a) make said chain triacontanol amine solution and the strong-base anion-exchange resin that the highly acid anion is had high adsorption in the first area;
(b) make from the chain triacontanol amine solution of said first area and the strong-base anion-exchange resin that acidulous anion is had high adsorption at second area;
(c) measure and write down electrical conductivity from the chain triacontanol amine solution of said first area;
(d) when the electrical conductivity from the chain triacontanol amine solution of said first area shows that highly acid anion in the said solution separates, from said system, remove said first area;
(e) measure and write down electrical conductivity from the chain triacontanol amine solution of said second area;
(f) when the electrical conductivity from the chain triacontanol amine solution of said second area shows that highly acid anion in the said solution separates, from said system, remove said second area;
(g) the said strong-base anion-exchange resin in said two zones is regenerated.
The strong-base anion-exchange resin that specifically discloses in this patent application in the said first area is the styrene-divinylbenzene skeleton resin with quaternary amine base, and the strong-base anion-exchange resin in the said second area is the styrene-divinylbenzene skeleton resin with alkanol quaternary amine base.
Disclose the method that a kind of strong-base anion-exchange resin purifies deterioration amine liquid among the CN1733355A, wherein, this method may further comprise the steps:
A, absorption: with temperature be 30-60 ℃ and through deterioration amine flow that filter to handle through being filled with the resin bed of strong-base anion-exchange resin, the heat stable salts anion in the resin adsorption deterioration amine liquid is that deterioration amine liquid is purified;
B, regeneration: after treating that resin adsorption in the said resin bed is saturated, washing said resin bed with alkali metal hydroxide aqueous solution, is that the resin in the said resin bed obtains regeneration and recovers adsorption capacity basically;
C, repetition above-mentioned steps a and step b;
D, recovery: after whenever carrying out above-mentioned steps a and step b circulation 50-200 time, wash said resin bed, remove the organic matter and the stronger SCN of affinity that are adsorbed on the resin with sodium-chloride water solution
-, to keep the ion exchange capacity of resin.
Specifically disclosing said strong-base anion-exchange resin in this patent application is I type styrene-divinylbenzene skeleton strong-base anion-exchange resin, II type styrene-divinylbenzene skeleton strong-base anion-exchange resin or acrylic backbone strong-base anion-exchange resin.
A kind of renovation process of inferior sulfolane is disclosed among the CN 1230545A, wherein, said method comprise with inferior sulfolane under 25-40 ℃ with 1-5 rice/hour linear flow speed pass through anion exchange resin layer.Concrete, said anion exchange resin is macroporous weakly basic anion exchange resin, and said macroporous weakly basic anion exchange resin is specially macropore polystyrene-NH
2Type or-N (CH
3)
2The type resin.
Though disclosed anion exchange resin all has certain adsorption capacity to the acidic anionic of the heat stable salts in the desulfurizing agent in the above-mentioned patent application; Yet; Said anion exchange resin is still not enough to the adsorption capacity of the acidic anionic of the heat stable salts in the said desulfurizing agent, can not be used for the desulfurizing agent that contains a large amount of sulfate ions is carried out Regeneration Treatment.
Summary of the invention
The objective of the invention is the above-mentioned defective for the renovation process that overcomes existing desulfurizing agent, a kind of renovation process of new desulfurizing agent is provided, the desulfurizing agent that adopts the renovation process of this desulfurizing agent to can be used in containing a large amount of sulfate ions carries out Regeneration Treatment.
The invention provides a kind of renovation process of desulfurizing agent; This method comprises that the desulfurizing agent that makes with obtaining after the mist that contains sulfur dioxide contacts contacts with anion exchange resin; Wherein, said anion exchange resin is the alkalescent epoxy type anion exchange resin.
Generally, owing to contain sulfur dioxide, sulfur trioxide, hydrogen chloride etc. in the sinter fume, particularly, the sinter fume that obtains in the metallurgy industry contains 3000-5000mg/m usually
3Sulfur dioxide, sulfur trioxide concentration is 100-350mg/m
3, hydrogen cloride concentration is 50-100mg/m
3And degraded at high temperature takes place and produces C in desulfurizing agent easily
2O
4 2-, therefore, sinter fume is with after desulfurizing agent contacts, thereby mainly contains C in the deterioration desulfurizing agent that obtains
2O
4 2-, SO
4 2-And Cl
-, and C
2O
4 2-, SO
4 2-And Cl
-Total concentration be generally the 1.2-1.5 mol, concrete SO
4 2-Concentration be the 1-1.2 mol.When heat stable salt total concentration in the desulfurizing agent during in the 1-1.5 mol, the desulphurizing ability of desulfurizing agent can obviously reduce.Simultaneously; Flue dust in the sinter fume with process that desulfurizing agent contacts in can be scattered in the desulfurizing agent, thereby form suspension, when the concentration of said suspension is big; Make the desulphurization system of desulfurizing agent reclaim equiment and desulfurizing agent recycling cause obstruction easily; Therefore, suspension and the heat stable salt that need treat in the recycling desulfurizer remove, thereby make said desulfurizing agent be able to regeneration.This area it has been generally acknowledged that through the active cation exchange groups that changes anion exchange resin can improve said anion exchange resin to C
2O
4 2-, SO
4 2-And Cl
-Deng adsorption capacity, yet, in the present invention, through selecting the fertile material of suitable anion exchange resin, thereby can significantly improve said anion exchange resin to part acid ion such as C
2O
4 2-, SO
4 2-And Cl
-Deng adsorption capacity.Concrete, inventor of the present invention finds that through the research back alkalescent epoxy type anion exchange resin is to C
2O
4 2-, SO
4 2-And Cl
-Has very strong adsorption capacity, particularly to SO
4 2-Have very strong adsorption capacity, therefore, the alkalescent epoxy type anion exchange resin is suitable for containing a large amount of SO
4 2-Desulfurizing agent carry out Regeneration Treatment.
Detect through experiment and to learn, the anion such as the C of the sta-salt of the renovation process of desulfurizing agent provided by the invention in can the effective elimination desulfurizing agent
2O
4 2-, SO
4 2-And Cl
-Thereby, remove the heat stable salt in the desulfurizing agent, and then make said desulfurizing agent obtain regeneration.
The specific embodiment
The renovation process of desulfurizing agent provided by the invention comprises that the desulfurizing agent that makes with obtaining after the mist that contains sulfur dioxide contacts contacts with anion exchange resin, and wherein, said anion exchange resin is the alkalescent epoxy type anion exchange resin.
In said method provided by the invention; Said do not have special qualification with the desulfurizing agent that obtains after the mist that contains sulfur dioxide contacts with the method that said alkalescent epoxy type anion exchange resin contacts; Can adopt conventional method to implement; For example can make the ion exchange resin bed of said desulfurizing agent, thereby realize said desulfurizing agent being carried out Regeneration Treatment with the mode of continous way through forming by said alkalescent epoxy type anion exchange resin; Also can under agitation said alkalescent epoxy type anion exchange resin be added in the said desulfurizing agent, thereby said desulfurizing agent carried out Regeneration Treatment with step mode.
Mode adopting continous way is carried out said desulfurizing agent under the situation of Regeneration Treatment, and said desulfurizing agent can comprise with the condition that said alkalescent epoxy type anion exchange resin contacts: temperature is 20-80 ℃, is preferably 30-60 ℃; The pH value is 3-9, is preferably 4.5-6.5; Volume space velocity is 0.1-5h
-1, be preferably 0.5-3h
-1Said pH value is meant the pH value of said desulfurizing agent before contacting with said alkalescent epoxy type anion exchange resin.
Adopting step method said desulfurizing agent to be carried out under the situation of Regeneration Treatment, said desulfurizing agent can comprise with the condition that said alkalescent epoxy type anion exchange resin contacts: temperature is 20-80 ℃, is preferably 30-60 ℃; The pH value is 3-9, is preferably 4.5-6.5; Time is 0.5-5 hour, is preferably 1-3 hour; With respect to 1 liter said desulfurizing agent, the consumption of said alkalescent epoxy type anion exchange resin is the 100-500 gram, is preferably the 200-400 gram.Said pH value is meant the pH value of said desulfurizing agent before contacting with said alkalescent epoxy type anion exchange resin.
In the present invention; When the renovation process of said desulfurizing agent also is included in the saturated absorption of said alkalescent epoxy type anion exchange resin; Solution with alkali metal hydroxide washes said alkalescent epoxy type anion exchange resin, thereby makes said alkalescent epoxy type anion exchange resin obtain regeneration and the basic adsorption capacity of recovering.
In the present invention; Said desulfurizing agent is carried out under the situation of Regeneration Treatment in the step method of employing; As long as make said desulfurizing agent and said alkalescent epoxy type anion exchange resin after implementing completion under the above-mentioned batch (-type) contact conditions, judge that promptly said alkalescent epoxy type anion exchange resin absorption is saturated.
The mode that adopts continous way said desulfurizing agent is carried out under the situation of Regeneration Treatment; Can through measure contact with said alkalescent epoxy type anion exchange resin preceding with contact after the pH value of liquid judge the degree of absorption of said alkalescent epoxy type anion exchange resin; When the difference of the pH value of the liquid before the pH of the liquid after said contact value and said the contact less than 1 the time, i.e. the said anion exchange resin absorption of decidable is saturated.
The solution of said alkali metal hydroxide does not have special qualification; Conventional NaOH, the potassium hydroxide solution that uses all can be used among the present invention; Under the preferable case; The solution of said alkali metal hydroxide is that concentration is the sodium hydroxide solution of 1-15 weight %, further is preferably the sodium hydroxide solution of 3-10 weight %.
Of the present invention a kind of preferred embodiment in; When the saturated absorption of said alkalescent epoxy type anion exchange resin, the operation cycle of regenerating with the alkali metal hydrogen sodium hydroxide solution are then carried out 50-80 time; Adopt the sodium chloride solution of 1-10 weight % that said anion exchange resin is recovered, the concrete method that said anion exchange resin is recovered has been conventionally known to one of skill in the art.
In the present invention, said alkalescent epoxy type anion exchange resin can be various chloro expoxy propane and polyethylene polyamine polycondensation at high temperature form have primary amine, secondary amine, tertiary amine and a quaternary amine (NH
2,=NH, ≡ N ,=one or more weak-base anion-exchange resin in N=); Can be commercially available; Particularly, said alkalescent epoxy type anion exchange resin can be 330 alkalescent epoxy type anion exchange resins and/or the 331 alkalescent epoxy type anion exchange resins of selling on the market.The active cation exchange groups of said alkalescent epoxy type anion exchange resin is one or more in primary amine groups, secondary amine, tertiary amine groups and the quaternary amine base; And the total exchange capacity of said alkalescent epoxy type anion exchange resin can be preferably 9-15mmol/g for greater than 9mmol/g.
In the present invention; The renovation process of said desulfurizing agent is mainly used in carrying out Regeneration Treatment with desulfurizing agent after the mist that contains sulfur dioxide contacts; Concrete; The desulfurizing agent that is used for removing the sulfur dioxide of the mist that contains sulfur dioxide does not have special qualification in the present invention, can be the conventional various desulfurizing agents that use in this area, and for example said desulfurizing agent can be for containing main absorbent components, activator and aqueous acid; Said main absorbent components can be in alkyl piperazine, hydroxyalkyl piperazine and the hydroxyalkyl piperazine ketone one or more, and said activator can be piperazine and diazabicylo.In said desulfurizing agent; Gross weight with this desulfurizing agent is a benchmark, and the content of said main absorbent components can be 3-50 weight %, and the content of said activator can be 0.5-15 weight %; The content of water can be 30-95 weight %, and the content of said acid makes the pH value of desulfurizing agent be 5-7.The said mist that contains sulfur dioxide does not have special qualification in the present invention yet; In the renovation process of said desulfurizing agent provided by the invention; Because the anion exchange resin (alkalescent epoxy type anion exchange resin) that is adopted has very strong absorption property to sulfate anion; Therefore, in the present invention, the said mist that contains sulfur dioxide is preferably especially and contains 3000-5000mg/m
3The sinter fume of sulfur dioxide.
Below through embodiment and Comparative Examples the present invention is done further detailed explanation.The 330 alkalescent epoxy type anion exchange resins that in following examples and Comparative Examples, adopted all originate in Anhui Samsung resin Co., Ltd, and its total exchange capacity is 9mmol/g; 331 alkalescent epoxy type anion exchange resins all originate in Anhui Province company of Wan Dong resin processing plant, and its total exchange capacity is 10mmol/g; 311 macroreticular weakly base acrylic acid type anion exchange resins originate in Anhui Samsung resin Co., Ltd, and its total exchange capacity is 7mmol/g; D301 alkalescent propenyl benzene series anion exchange resin originates in Anhui Samsung resin Co., Ltd, and its total exchange capacity is 4.8mmol/g; D296 macroporous strong basic benzene diene series-N=(CH
3)
3The type resin originates in Tianjin Nankai and resin Co., Ltd, and its total exchange capacity is 3.6mmol/g; D301R macroreticular weakly base polystyrene-N (CH
3)
2The type resin originates in Tianjin Nankai and resin Co., Ltd, and its total exchange capacity is 4.8mmol/g; D301T macroreticular weakly base polystyrene-N (CH
3)
2The type resin originates in Tianjin Nankai and resin Co., Ltd, and its total exchange capacity is 9.5mmol/g.
Preparation example 1
(1) preparation desulfurizing agent
With 80 gram N-hydroxyethyl piperazines, 30 gram N, N-diethyl piperazine, 40 gram diazabicylos, 50 gram piperazines are added in 400 ml waters, adopt the pH of the phosphoric acid solution regulator solution of 1mol/L; Stir; Constant volume is controlled the pH=6.5 of solution, thereby is obtained desulfurizing agent to 1000ml then.
(2) preparation simulation deterioration desulfurizing agent
The desulfurizing agent that makes in (1) is heated to 50 ℃, makes said desulfurizing agent then and contain 4000mg/m
3The mist of sulfur dioxide is 0.5kg/Nm with the liquid-gas ratio in the absorption tower
3Carry out counter current contacting, thereby obtain the desulfurization rich solution; Then, the said desulfurization rich solution that obtains is put into there-necked flask, a bite is plugged in thermometer, and a bite is inserted fume pipe and led to the bottom of desulfurization rich solution, in fume pipe, feeds nitrogen, and the speed of feeding is 2 * 10
-4Nm
3/ min, the time of feeding is 80 minutes, is heated to 100 ℃ simultaneously, makes the sulfur dioxide desorption of absorption, thereby obtains containing the simulation deterioration desulfurizing agent of heat stable salt, the pH value of said simulation deterioration desulfurizing agent is 6.Adopt the mercuric nitrate complexometry method to measure the chlorine ion concentration in the said simulation deterioration desulfurizing agent; Adopt the concentration of the oxalate denominationby in the said simulation deterioration of the ion-chromatographic determination desulfurizing agent; Adopt the concentration of the sulfate ion in the said simulation deterioration of the gravimetric detemination desulfurizing agent, its result is as shown in table 1 below.
Table 1
| SO 4 2- | C 2O 4 2- | Cl - | |
| Concentration (mol/L) | 0.8 | 0.15 | 0.4 |
Embodiment 1
Present embodiment is used to explain the renovation process of said desulfurizing agent provided by the invention.
The sodium hydroxide solution that makes 2 weight % is with 2h
-1Volume space velocity (resin bed is that 330 alkalescent epoxies of 0.5-1.2 millimeter are that exchanger resin forms by particle diameter through the resin bed processed of 300 grams, 330 alkalescent epoxy type anion exchange resins is housed; The height of said resin bed is 33.6 centimetres), then with deionized water to said resin bed with 0.5h
-1Volume space velocity wash.Then, under 50 ℃, making the said simulation deterioration desulfurizing agent that makes in the preparation example 1 is 3h with the volume space velocity
-1Through said resin bed; And adopt the mercuric nitrate complexometry method to measure through the chlorine ion concentration in the desulfurizing agent after the said resin bed; Adopt the concentration of ion-chromatographic determination through the oxalate denominationby in the desulfurizing agent after the said resin bed; Adopt the concentration of gravimetric detemination through the sulfate ion in the desulfurizing agent after the said resin bed; And calculating the adsorption capacity of said alkalescent epoxy type anion exchange resin respectively to oxalate denominationby, sulfate ion and chlorion, its result is as shown in table 2 below.
Embodiment 2
Present embodiment is used to explain the renovation process of said desulfurizing agent provided by the invention.
The sodium hydroxide solution that makes 2 weight % is with 2h
-1Volume space velocity (resin bed is that 331 alkalescent epoxies of 0.1-1.1 millimeter are that exchanger resin forms by particle diameter through the resin bed processed of 300 grams, 331 alkalescent epoxy type anion exchange resins is housed; The height of said resin bed is 34.8 centimetres), then with deionized water to said resin bed with 1h
-1Volume space velocity wash.Then, under 30 ℃, making the said simulation deterioration desulfurizing agent that makes in the preparation example 1 is 2h with the volume space velocity
-1Through said resin bed; And adopt the mercuric nitrate complexometry method to measure through the chlorine ion concentration in the desulfurizing agent after the said resin bed; Adopt the concentration of ion-chromatographic determination through the oxalate denominationby in the desulfurizing agent after the said resin bed; Adopt the concentration of gravimetric detemination through the sulfate ion in the desulfurizing agent after the said resin bed; And calculating the adsorption capacity of said alkalescent epoxy type anion exchange resin respectively to oxalate denominationby, sulfate ion and chlorion, its result is as shown in table 2 below.
Embodiment 3
Present embodiment is used to explain the renovation process of said desulfurizing agent provided by the invention.
The sodium hydroxide solution that makes 2 weight % is with 2h
-1Volume space velocity (resin bed is that 330 alkalescent epoxies of 0.6-1.5 millimeter are that exchanger resin forms by particle diameter through the resin bed processed of 300 grams, 330 alkalescent epoxy type anion exchange resins is housed; The height of said resin bed is 33.6 centimetres), then with deionized water to said resin bed with 2h
-1Volume space velocity wash.Then, under 60 ℃, making the said simulation deterioration desulfurizing agent that makes in the preparation example 1 is 1.0h with the volume space velocity
-1Through said resin bed; And adopt the mercuric nitrate complexometry method to measure through the chlorine ion concentration in the desulfurizing agent after the said resin bed; Adopt the concentration of ion-chromatographic determination through the oxalate denominationby in the desulfurizing agent after the said resin bed; Adopt the concentration of gravimetric detemination through the sulfate ion in the desulfurizing agent after the said resin bed; And calculating the adsorption capacity of said alkalescent epoxy type anion exchange resin respectively to oxalate denominationby, sulfate ion and chlorion, its result is as shown in table 2 below.
Comparative Examples 1-5
Method according to embodiment 1 is carried out Regeneration Treatment to preparing the desulfurizing agent that obtains in the example 1; Different is to load 300 grams, 311 macroreticular weakly base acrylic acid type anion exchange resins, D301 alkalescent propenyl benzene series anion exchange resin, D296 macroporous strong basic benzene diene series-N=(CH respectively
3)
3Type resin, D301R macroreticular weakly base polystyrene-N (CH
3)
2Type resin and D301T macroreticular weakly base polystyrene-N (CH
3)
2The resin bed of type resin replaces the resin bed of 330 alkalescent epoxy type anion exchange resins wherein.Measure concentration, the concentration of oxalate denominationby and the concentration of chlorion according to the method for embodiment 1 through sulfate ion in the desulfurizing agent after the said resin bed; And calculating the adsorption capacity of said anion exchange resin respectively to oxalate denominationby, sulfate ion and chlorion, its result is as shown in table 2 below.
Table 2
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | Comparative Examples 4 | Comparative Examples 5 | |
| The resin kind | 330 alkalescent epoxy type anion exchange resins | 331 alkalescent epoxy type anion exchange resins | 330 alkalescent epoxy type anion exchange resins | 311 macroreticular weakly base acrylic acid type anion exchange resins | D301 alkalescent propenyl benzene series anion exchange resin | D296 macroporous strong basic benzene diene series-N=(CH 3) 3The type resin | D301R macroreticular weakly base polystyrene-N (CH 3) 2The type resin | D301T macroreticular weakly base polystyrene-N (CH 3) 2The type resin |
| SO 4 2-Adsorption capacity (g/300g) | 24.64 | 23.15 | 25.74 | 18.45 | 16.42 | 10.11 | 13.82 | 15.87 |
| Cl -Adsorption capacity (g/300g) | 5.81 | 5.18 | 6.41 | 2.95 | 2.16 | 3.24 | 1.93 | 1.75 |
| C 2O 4 2-Adsorption capacity (g/300g) | 2.15 | 1.96 | 2.45 | 0.28 | 1.02 | 2.17 | 0.84 | 0.97 |
Data by table 2 can be found out, in the renovation process of desulfurizing agent provided by the invention, owing to employing alkalescent epoxy type anion exchange resin, thereby show the SO in the desulfurizing agent
4 2-, C
2O
4 2-, Cl
-All has very strong adsorption effect.
Embodiment 4
Present embodiment is used to explain the renovation process of said desulfurizing agent provided by the invention.
330 alkalescent epoxy type anion exchange resins are immersed in 4h in the sodium hydroxide solution of 2 weight %, use deionized water that said 330 alkalescent epoxy type anion exchange resins are washed to the pH value then and be 7-8.
Getting 10 grams, through the exchange of 330 alkalescent epoxy series anions after above-mentioned processing tree it to be joined solution temperature be in the simulation deterioration desulfurizing agent that makes in 30 ℃ 100 milliliters the preparation example 1; After under condition of stirring, reacting 5 hours; The concentration of chlorion in the said desulfurizing agent behind the employing mercuric nitrate complexometry method assaying reaction; Adopt the concentration of the reacted said desulfurizing agent mesoxalic acid radical ion of ion-chromatographic determination; Adopt the concentration of sulfate ion in the reacted said desulfurizing agent of gravimetric detemination, and calculate the adsorption capacity of said ion exchange resin to oxalate denominationby, sulfate ion and chlorion respectively, its result is as shown in table 3 below.
Comparative Examples 6-10
Method according to embodiment 4 is carried out Regeneration Treatment to preparing the simulation desulfurizing agent that obtains in the example 1; Different is to use 311 macroreticular weakly base acrylic acid type anion exchange resins, D301 alkalescent propenyl benzene series anion exchange resin, D296 macroporous strong basic benzene diene series-N=(CH respectively
3)
3Type resin, D301R macroreticular weakly base polystyrene-N (CH
3)
2Type resin and D301T macroreticular weakly base polystyrene-N (CH
3)
2The type resin replaces 330 alkalescent epoxy type anion exchange resins wherein.Adopt concentration, the concentration of oxalate denominationby and the concentration of chlorion of sulfate ion in the said desulfurizing agent behind the method assaying reaction identical with embodiment 4; Calculate the adsorption capacity of said anion exchange resin to oxalate denominationby, sulfate ion and chlorion then respectively, its result is as shown in table 3 below.
Table 3
| Embodiment 4 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | Comparative Examples 4 | Comparative Examples 5 | |
| The resin kind | 330 alkalescent epoxy type anion exchange resins | 311 macroreticular weakly base acrylic acid type anion exchange resins | D301 alkalescent propenyl benzene series anion exchange resin | D296 macroporous strong basic benzene diene series-N=(CH 3) 3The type resin | D301R macroreticular weakly base polystyrene-N (CH 3) 2The type resin | D301T macroreticular weakly base polystyrene-N (CH 3) 2The type resin |
| SO 4 2-Adsorption capacity (g/10g) | 0.879 | 0.672 | 0.581 | 0.357 | 0.476 | 0.545 |
| Cl -Adsorption capacity (g/10g) | 0.224 | 0.104 | 0.085 | 0.122 | 0.076 | 0.068 |
| C 2O 4 2-Adsorption capacity (g/10g) | 0.088 | 0.011 | 0.038 | 0.085 | 0.031 | 0.035 |
Data by table 3 can be found out, in the renovation process of desulfurizing agent provided by the invention, owing to employing alkalescent epoxy type anion exchange resin, thereby show the SO in the desulfurizing agent
4 2-, C
2O
4 2-And Cl
-All has very strong adsorption effect.
This shows, adopt the renovation process of said desulfurizing agent provided by the invention can effectively remove the SO in the desulfurizing agent
4 2-, C
2O
4 2-And Cl
-
Claims (7)
1. the renovation process of a desulfurizing agent; This method comprises that the desulfurizing agent that makes with obtaining after the mist that contains sulfur dioxide contacts contacts with anion exchange resin; It is characterized in that; Said anion exchange resin is the alkalescent epoxy type anion exchange resin; The active cation exchange groups of said alkalescent epoxy type anion exchange resin is one or more in primary amine groups, secondary amine, tertiary amine groups and the quaternary amine base, and the total exchange capacity of said alkalescent epoxy type anion exchange resin is 9-15mmol/g, and the said mist that contains sulfur dioxide is for containing 3000-5000mg/m
3The sinter fume of sulfur dioxide;
The method that said desulfurizing agent contacts with said alkalescent epoxy type anion exchange resin comprises makes the ion exchange resin bed of said desulfurizing agent through being formed by said alkalescent epoxy type anion exchange resin; The contact conditions of said desulfurizing agent and said alkalescent epoxy type anion exchange resin comprises: temperature is 20-80 ℃; The pH value is 3-9, and volume space velocity is 0.1-5h
-1
2. method according to claim 1, wherein, the contact conditions of said desulfurizing agent and said alkalescent epoxy type anion exchange resin comprises: temperature is 30-60 ℃, and the pH value is 4.5-6.5, and volume space velocity is 0.5-3h
-1
3. method according to claim 1 and 2 wherein, when said method also is included in the saturated absorption of said alkalescent epoxy type anion exchange resin, is washed said alkalescent epoxy type anion exchange resin with the solution of alkali metal hydroxide.
4. method according to claim 3, wherein, the concentration of the solution of said alkali metal hydroxide is 1-15 weight %.
5. the renovation process of a desulfurizing agent; This method comprises that the desulfurizing agent that makes with obtaining after the mist that contains sulfur dioxide contacts contacts with anion exchange resin; It is characterized in that; Said anion exchange resin is the alkalescent epoxy type anion exchange resin; The active cation exchange groups of said alkalescent epoxy type anion exchange resin is one or more in primary amine groups, secondary amine, tertiary amine groups and the quaternary amine base, and the total exchange capacity of said alkalescent epoxy type anion exchange resin is 9-15mmol/g, and the said mist that contains sulfur dioxide is for containing 3000-5000mg/m
3The sinter fume of sulfur dioxide;
The method that said desulfurizing agent contacts with said alkalescent epoxy type anion exchange resin comprises said desulfurizing agent is added in the said alkalescent epoxy type anion exchange resin; The contact conditions of said desulfurizing agent and said alkalescent epoxy type anion exchange resin comprises: temperature is 20-80 ℃; The pH value is 3-9; Time is 0.5-5 hour, and with respect to 1 liter said desulfurizing agent, the consumption of said alkalescent epoxy type anion exchange resin is the 100-500 gram.
6. method according to claim 5 wherein, when said method also is included in the saturated absorption of said alkalescent epoxy type anion exchange resin, is washed said alkalescent epoxy type anion exchange resin with the solution of alkali metal hydroxide.
7. method according to claim 6, wherein, the concentration of the solution of said alkali metal hydroxide is 1-15 weight %.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102254228A CN101874981B (en) | 2009-12-10 | 2009-12-10 | Method for regenerating desulfurizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN2009102254228A CN101874981B (en) | 2009-12-10 | 2009-12-10 | Method for regenerating desulfurizer |
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| CN102423617A (en) * | 2011-09-01 | 2012-04-25 | 湖南湘达环保工程有限公司 | Method of preventing scaling of desulphurization equipment and pipelines used in dual-alkali desulphurization process |
| CN102908806B (en) * | 2012-11-08 | 2015-02-04 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for removing heat-stable salt in flue gas desulfurization solution by normal-pressure ion exchanger |
| CN105498539B (en) * | 2016-01-20 | 2017-06-16 | 西北大学 | A kind of method for recycling of fume desulfurizing agent |
| CN105597512B (en) * | 2016-01-20 | 2017-06-16 | 西北大学 | A kind of renovation process of fume desulfurizing agent |
| CN109453825A (en) * | 2018-09-07 | 2019-03-12 | 中国石油化工股份有限公司 | A kind of commercial plant and application method reducing the corrosion of hydramine depriving hydrogen sulphide system equipment |
| CN109173727B (en) * | 2018-10-31 | 2021-09-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for regenerating ineffective complexing denitration agent |
| CN115990394B (en) * | 2023-03-24 | 2023-06-02 | 成都益志科技有限责任公司 | Desalination and sodium removal system and method in ionic liquid desulfurization |
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| US4170628A (en) * | 1977-03-25 | 1979-10-09 | Union Carbide Corporation | Process for removing SO2 from effluent gases and for removing heat stable salts from systems in which they accumulate using an anion exchange resin |
| CN101083343A (en) * | 2006-06-02 | 2007-12-05 | 比亚迪股份有限公司 | Electrolysing solution acid stripping method and apparatus |
| CN101507932A (en) * | 2008-11-09 | 2009-08-19 | 中国船舶重工集团公司第七一八研究所 | Preparation method of material capable of removing hydrogen sulphide and thiol |
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