CN101874981A - Method for regenerating desulfurizer - Google Patents
Method for regenerating desulfurizer Download PDFInfo
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- CN101874981A CN101874981A CN2009102254228A CN200910225422A CN101874981A CN 101874981 A CN101874981 A CN 101874981A CN 2009102254228 A CN2009102254228 A CN 2009102254228A CN 200910225422 A CN200910225422 A CN 200910225422A CN 101874981 A CN101874981 A CN 101874981A
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- desulfurizing agent
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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, carry out heating desorption then in desorber, the sour gas that discharges high concentration is recycled, and the amine liquid that obtains after the desorb simultaneously can reuse after handling through regeneration.
Oxygen content is very high in the sinter fume, there is the oxidative degradation of three kinds of degraded modes such as organic amine aqueous solution in the organic amine desulfuration solution in to the process of sintering flue gas desulfurization, the chemical degradation of the thermal degradation of organic amine solution and organic amine solution, organic amine can generate formate through after the above-mentioned degraded, acetate, organic acids such as oxalate, 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, the sulfite ion in the sweetening liq can partial oxidation be a sulfate ion simultaneously; In addition, above-mentioned organic anion, inorganic anion can combine with organic amine generate can not desorb in desorber thermal-stable salt, when the content of thermal-stable salt reached certain amount, described 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 described chain triacontanol amine solution, described method comprises:
(a) make described 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 described first area and the strong-base anion-exchange resin that acidulous anion is had high adsorption at second area;
(c) measurement and record are from the electrical conductivity of the chain triacontanol amine solution of described first area;
(d) when the electrical conductivity from the chain triacontanol amine solution of described first area shows that highly acid anion in the described solution separates, from described system, remove described first area;
(e) measurement and record are from the electrical conductivity of the chain triacontanol amine solution of described second area;
(f) when the electrical conductivity from the chain triacontanol amine solution of described second area shows that highly acid anion in the described solution separates, from described system, remove described second area;
(g) the described strong-base anion-exchange resin in described two zones is regenerated.
The strong-base anion-exchange resin that specifically discloses in this patent application in the described first area is the styrene-divinylbenzene skeleton resin with quaternary amine base, and the strong-base anion-exchange resin in the described 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 is that 30-60 ℃ and the deterioration amine liquid handled are after filtration flowed through and is filled with the resin bed of strong-base anion-exchange resin, and 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 described resin bed is saturated, washing described resin bed with alkali metal hydroxide aqueous solution, is that the resin in the described resin bed obtains regeneration and recovers adsorption capacity substantially;
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 described 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 described 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, described method comprise with inferior sulfolane under 25-40 ℃ with 1-5 rice/hour linear flow speed pass through anion exchange resin layer.Concrete, described anion exchange resin is macroporous weakly basic anion exchange resin, and described 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, described anion exchange resin is still not enough to the adsorption capacity of the acidic anionic of the heat stable salts in the described desulfurizing agent, can not be used for the desulfurizing agent that the contains a large amount of sulfate ions processing of regenerating.
Summary of the invention
The objective of the invention is above-mentioned defective, a kind of renovation process of new desulfurizing agent is provided, adopt the renovation process of this desulfurizing agent to can be used in the desulfurizing agent that the contains a large amount of sulfate ions processing of regenerating for the renovation process that overcomes existing desulfurizing agent.
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, described 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 formation suspension, when the concentration of described 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 described desulfurizing agent is regenerated.This area it has been generally acknowledged that by the active cation exchange groups that changes anion exchange resin can improve described anion exchange resin to C
2O
4 2-, SO
4 2-And Cl
-Deng adsorption capacity, yet, in the present invention, by selecting the fertile material of suitable anion exchange resin, thereby can significantly improve described anion exchange resin to part acid ion such as C
2O
4 2-, SO
4 2-And Cl
-Deng adsorption capacity.Concrete, the present inventor finds that by 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-The desulfurizing agent processing of regenerating.
Detect by experiment and learn that the renovation process of desulfurizing agent provided by the invention can effectively remove the anion such as the C of the sta-salt in the desulfurizing agent
2O
4 2-, SO
4 2-And Cl
-Thereby, remove the heat stable salt in the desulfurizing agent, and then make described 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, described anion exchange resin is the alkalescent epoxy type anion exchange resin.
In described method provided by the invention, there is no particular limitation for the method that described and the desulfurizing agent that obtains after the mist that contains sulfur dioxide contacts contact with described alkalescent epoxy type anion exchange resin, can adopt conventional method to implement, for example can make the ion exchange resin bed of described desulfurizing agent by forming by described alkalescent epoxy type anion exchange resin, thus realization in the mode of continous way to the processing of regenerating of described desulfurizing agent; Also can under agitation described alkalescent epoxy type anion exchange resin be added in the described desulfurizing agent, thus in step mode to the processing of regenerating of described desulfurizing agent.
The mode that adopts continous way was regenerated situation about handling to described desulfurizing agent under, described desulfurizing agent can comprise with the condition that described alkalescent epoxy type anion exchange resin contacts: temperature was 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
-1Described pH value be meant described desulfurizing agent with pH value before described alkalescent epoxy type anion exchange resin contacts.
The step method of employing was regenerated situation about handling to described desulfurizing agent under, described desulfurizing agent can comprise with the condition that described alkalescent epoxy type anion exchange resin contacts: temperature was 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 described desulfurizing agent, the consumption of described alkalescent epoxy type anion exchange resin is the 100-500 gram, is preferably the 200-400 gram.Described pH value be meant described desulfurizing agent with pH value before described alkalescent epoxy type anion exchange resin contacts.
In the present invention, when the renovation process of described desulfurizing agent also is included in the saturated absorption of described alkalescent epoxy type anion exchange resin, solution with alkali metal hydroxide washes described alkalescent epoxy type anion exchange resin, thereby makes described alkalescent epoxy type anion exchange resin obtain regeneration and the basic adsorption capacity of recovering.
In the present invention, the step method of employing is regenerated situation about handling to described desulfurizing agent under, as long as make described desulfurizing agent and described alkalescent epoxy type anion exchange resin after implementing to finish under the above-mentioned batch (-type) contact conditions, judge that promptly described alkalescent epoxy type anion exchange resin absorption is saturated.
Under the situation about handling that described desulfurizing agent is regenerated of the mode that adopts continous way, can by measure contact with described alkalescent epoxy type anion exchange resin preceding with contact after the pH value of liquid judge the degree of absorption of described alkalescent epoxy type anion exchange resin, when the difference of the pH value of the liquid before the pH of the liquid after described contact value and described the contact less than 1 the time, i.e. the described anion exchange resin absorption of decidable is saturated.
There is no particular limitation for the solution of described alkali metal hydroxide, conventional NaOH, the potassium hydroxide solution that uses all can be used among the present invention, under the preferable case, the solution of described alkali metal hydroxide is that concentration is the sodium hydroxide solution of 1-15 weight %, more preferably the sodium hydroxide solution of 3-10 weight %.
Of the present invention a kind of preferred embodiment in, when the saturated absorption of described 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 described anion exchange resin is recovered, the concrete method that described anion exchange resin is recovered has been conventionally known to one of skill in the art.
In the present invention, described 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, described 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 described 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 described 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 described desulfurizing agent be mainly used in to the processing of regenerating of the desulfurizing agent after the mist that contains sulfur dioxide contacts, concrete, there is no particular limitation in the present invention to be used for removing the desulfurizing agent of sulfur dioxide of the mist that contains sulfur dioxide, can be the conventional various desulfurizing agents that use in this area, for example described desulfurizing agent can be for containing main absorbent components, activator and aqueous acid, described main absorbent components can be alkyl piperazine, in hydroxyalkyl piperazine and the hydroxyalkyl piperazine ketone one or more, described activator can be piperazine and diazabicylo.In described desulfurizing agent, gross weight with this desulfurizing agent is a benchmark, and the content of described main absorbent components can be 3-50 weight %, and the content of described activator can be 0.5-15 weight %, the content of water can be 30-95 weight %, and the content of described acid makes the pH value of desulfurizing agent be 5-7.Also there is no particular limitation in the present invention for the described mist that contains sulfur dioxide, in the renovation process of described 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 described mist that contains sulfur dioxide is preferably especially and contains 3000-5000mg/m
3The sinter fume of sulfur dioxide.
The present invention is further detailed explanation with Comparative Examples by the following examples.The 330 alkalescent epoxy type anion exchange resins that adopted in the following Examples and Comparative Examples 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 described 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 described 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, feeds nitrogen in fume pipe, 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 described simulation deterioration desulfurizing agent is 6.Employing mercuric nitrate complexometry method is measured the chlorine ion concentration in the described simulation deterioration desulfurizing agent, adopt the concentration of the oxalate denominationby in the described simulation deterioration of the ion-chromatographic determination desulfurizing agent, adopt the concentration of the sulfate ion in the described 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 illustrate the renovation process of described 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 by the resin bed made of 300 grams, 330 alkalescent epoxy type anion exchange resins is housed, the height of described resin bed is 33.6 centimetres), then with deionized water to described resin bed with 0.5h
-1Volume space velocity wash.Then, making the described simulation deterioration desulfurizing agent that makes in the preparation example 1 under 50 ℃ is 3h with the volume space velocity
-1By described resin bed, and adopt the mercuric nitrate complexometry method to measure by the chlorine ion concentration in the desulfurizing agent after the described resin bed, adopt the concentration of ion-chromatographic determination by the oxalate denominationby in the desulfurizing agent after the described resin bed, adopt the concentration of gravimetric detemination by the sulfate ion in the desulfurizing agent after the described resin bed, and calculating the adsorption capacity of described 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 illustrate the renovation process of described 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 by the resin bed made of 300 grams, 331 alkalescent epoxy type anion exchange resins is housed, the height of described resin bed is 34.8 centimetres), then with deionized water to described resin bed with 1h
-1Volume space velocity wash.Then, making the described simulation deterioration desulfurizing agent that makes in the preparation example 1 under 30 ℃ is 2h with the volume space velocity
-1By described resin bed, and adopt the mercuric nitrate complexometry method to measure by the chlorine ion concentration in the desulfurizing agent after the described resin bed, adopt the concentration of ion-chromatographic determination by the oxalate denominationby in the desulfurizing agent after the described resin bed, adopt the concentration of gravimetric detemination by the sulfate ion in the desulfurizing agent after the described resin bed, and calculating the adsorption capacity of described 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 illustrate the renovation process of described 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 by the resin bed made of 300 grams, 330 alkalescent epoxy type anion exchange resins is housed, the height of described resin bed is 33.6 centimetres), then with deionized water to described resin bed with 2h
-1Volume space velocity wash.Then, making the described simulation deterioration desulfurizing agent that makes in the preparation example 1 under 60 ℃ is 1.0h with the volume space velocity
-1By described resin bed, and adopt the mercuric nitrate complexometry method to measure by the chlorine ion concentration in the desulfurizing agent after the described resin bed, adopt the concentration of ion-chromatographic determination by the oxalate denominationby in the desulfurizing agent after the described resin bed, adopt the concentration of gravimetric detemination by the sulfate ion in the desulfurizing agent after the described resin bed, and calculating the adsorption capacity of described 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
According to the method for embodiment 1 to the desulfurizing agent that obtains in the preparation example 1 processing of regenerating, 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 by sulfate ion in the described resin bed desulfurizing agent afterwards, and calculating the adsorption capacity of described 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 |
By the data of table 2 as can be seen, in the renovation process of desulfurizing agent provided by the invention, owing to adopt the alkalescent epoxy type anion exchange resin, thus 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 illustrate the renovation process of described 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 %, then with deionized water to described 330 alkalescent epoxy type anion exchange resins wash to the pH value 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 described desulfurizing agent behind the employing mercuric nitrate complexometry method assaying reaction, adopt the concentration of the reacted described desulfurizing agent mesoxalic acid radical ion of ion-chromatographic determination, adopt the concentration of sulfate ion in the reacted described desulfurizing agent of gravimetric detemination, and calculate described ion exchange resin respectively to oxalate denominationby, the adsorption capacity of sulfate ion and chlorion, its result is as shown in table 3 below.
Comparative Examples 6-10
According to the method for embodiment 4 to the simulation desulfurizing agent that obtains in the preparation example 1 processing of regenerating, 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 described desulfurizing agent behind the method assaying reaction identical with embodiment 4, calculate the adsorption capacity of described 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 |
By the data of table 3 as can be seen, in the renovation process of desulfurizing agent provided by the invention, owing to adopt the alkalescent epoxy type anion exchange resin, thus 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 described desulfurizing agent provided by the invention can effectively remove SO in the desulfurizing agent
4 2-, C
2O
4 2-And Cl
-
Claims (10)
1. the renovation process of a desulfurizing agent, this method comprise that the desulfurizing agent that makes with obtaining after the mist that contains sulfur dioxide contacts contacts with anion exchange resin, is characterized in that described anion exchange resin is the alkalescent epoxy type anion exchange resin.
2. method according to claim 1, wherein, the method that described desulfurizing agent contacts with described alkalescent epoxy type anion exchange resin comprises makes the ion exchange resin bed of described desulfurizing agent by being formed by described alkalescent epoxy type anion exchange resin.
3. method according to claim 2, wherein, the contact conditions of described desulfurizing agent and described alkalescent epoxy type anion exchange resin comprises: temperature is 20-80 ℃, and the pH value is 3-9, and volume space velocity is 0.1-5h
-1
4. method according to claim 3, wherein, the contact conditions of described desulfurizing agent and described 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
5. method according to claim 1, wherein, the method that described desulfurizing agent contacts with described alkalescent epoxy type anion exchange resin comprises described desulfurizing agent is added in the described alkalescent epoxy type anion exchange resin.
6. method according to claim 5, wherein, the contact conditions of described desulfurizing agent and described alkalescent epoxy type anion exchange resin comprises: temperature is 20-80 ℃, the pH value is 3-9, time is 0.5-5 hour, with respect to 1 liter described desulfurizing agent, the consumption of described alkalescent epoxy type anion exchange resin is the 100-500 gram.
7. according to any described method among the claim 1-6, wherein, the active cation exchange groups of described alkalescent epoxy type anion exchange resin is one or more in primary amine groups, secondary amine, tertiary amine groups and the quaternary amine base.
8. method according to claim 7, wherein, the total exchange capacity of described alkalescent epoxy type anion exchange resin is 9-15mmol/g.
9. method according to claim 1 wherein, when described method also is included in the saturated absorption of described alkalescent epoxy type anion exchange resin, is washed described alkalescent epoxy type anion exchange resin with the solution of alkali metal hydroxide.
10. method according to claim 9, wherein, the concentration of the solution of described alkali metal hydroxide is 1-15 weight %.
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|---|---|---|---|
| CN2009102254228A CN101874981B (en) | 2009-12-10 | 2009-12-10 | Method for regenerating desulfurizer |
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| CN2009102254228A CN101874981B (en) | 2009-12-10 | 2009-12-10 | Method for regenerating desulfurizer |
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| CN101874981A true CN101874981A (en) | 2010-11-03 |
| CN101874981B CN101874981B (en) | 2012-06-06 |
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| CN2009102254228A Expired - Fee Related CN101874981B (en) | 2009-12-10 | 2009-12-10 | Method for regenerating desulfurizer |
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Cited By (7)
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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 |
| CN102908806A (en) * | 2012-11-08 | 2013-02-06 | 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 |
| CN105597512A (en) * | 2016-01-20 | 2016-05-25 | 西北大学 | Regenerating method of flue gas desulfurization agent |
| CN105498539B (en) * | 2016-01-20 | 2017-06-16 | 西北大学 | A kind of method for recycling 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 |
| CN115990394A (en) * | 2023-03-24 | 2023-04-21 | 成都益志科技有限责任公司 | Desalination and sodium removal system and method in ionic liquid desulfurization |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101502742B (en) * | 2009-02-20 | 2011-09-07 | 中国石油化工集团公司 | Method for removing thermostable salt in amine liquid for desulphurization |
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2009
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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 |
| CN102908806A (en) * | 2012-11-08 | 2013-02-06 | 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 |
| 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 |
| CN105597512A (en) * | 2016-01-20 | 2016-05-25 | 西北大学 | Regenerating method of flue gas desulfurization agent |
| 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 |
| CN115990394A (en) * | 2023-03-24 | 2023-04-21 | 成都益志科技有限责任公司 | Desalination and sodium removal system and method in ionic liquid desulfurization |
| 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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