CN103341301A - Composite solution for sulphur dioxide absorption in membrane separation - Google Patents
Composite solution for sulphur dioxide absorption in membrane separation Download PDFInfo
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- CN103341301A CN103341301A CN2013102846316A CN201310284631A CN103341301A CN 103341301 A CN103341301 A CN 103341301A CN 2013102846316 A CN2013102846316 A CN 2013102846316A CN 201310284631 A CN201310284631 A CN 201310284631A CN 103341301 A CN103341301 A CN 103341301A
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Abstract
The invention relates to the field of liquid-gas separation, in particular relates to the field of smoke desulfuration, and more in particular relates to a composite solution for absorbing sulphur dioxide in mixed gas. The invention aims at providing a sulphur dioxide absorbent capable of being used for absorption for a membrane contactor. The smoke composite-type desulfurizer disclosed by the invention is composed of the aqueous solution of lactic acid salt and amino acid salt, wherein the mixing molar ratio of the lactic acid salt to the amino acid salt is 1: (0.5 to 2.2). The composite-type desulfurizer disclosed by the invention is good in chemical stability, low in foaminess and low in viscosity, and raw materials are abundant in source, easy to buy and low in price. A desulfuration process using the composite-type desulfurizer disclosed by the invention is high in mass transfer coefficient, undisturbed in gas-liquid flow, low in mass transfer resistance, high in desulfuration rate, convenient to operate, high in operation flexibility, free from secondary pollution, and capable of stably running in the membrane contactor.
Description
Technical field
The present invention relates to liquid gas separation field, particularly relate to the desulfuration field of flue gas, more specifically relate to a kind of composite solution that separates the sulfur dioxide absorption for film.
Background technology
SO in the flue gas such as coal-burning power plant, metallurgy industry
2Being one of atmosphere major pollutants, is the formation source of acid rain.Along with the raising day by day that environmental protection requires Air Pollutant Emission, in flue gas desulfurization purifies, how rationally to select sulfur removal technology for use, reach SO after the flue gas desulfurization with low investment and operating cost
2Discharge capacity meets the regulation of discharging standards, is flue gas desulfurization key of healthy development problems such as coal-burning power plant, metallurgy industry.Therefore, various high-performance SO
2The exploitation of absorbent is one of theme of this area research, and in recent years, composite absorber was because its particular performances has become the heat subject of acid gas absorbent research and development.
In flue gas desulfurization (Flue gas desulfurization the is called for short FGD) technology, the method common by the kind of desulfurizing agent has: with CaCO
3(lime stone) is the calcium method on basis, based on the magnesium method of MgO, with Na
2SO
3For the sodium method on basis, with NH
3Be the ammonia process on basis, based on organic alkaline process of organic base.Calcium method desulfur technology is adopted in commercialization flue gas desulfurization more than 90% in the world, and the calcium method is divided into wet method, dry method and half-dried (half is wet) method.Wet technique is to adopt solution or the slurries contain absorbent to handle sulfur-containing smoke gas, and this method has that desulphurization reaction speed is fast, equipment simple, the desulfuration efficiency advantages of higher, but the ubiquity seriously corroded, operation and maintenance cost is high and cause secondary pollution problems.Dry technique is that the processing of absorption process and product is all carried out under anhydrous state, this method has no spent acid sewage discharge, equipment corrosion is lighter, problems such as flue-gas temperature does not have advantages such as obvious reduction, secondary pollution are few, but exists desulfuration efficiency low, and reaction speed is slow, equipment is huge.The semidry method technology refers to desulfurizing agent desulfurization under drying regime, regeneration under wet condition (as washing active carbon regeneration flow process), perhaps desulfurization under wet condition, handles the flue gas desulfurization technique of desulfurization product (as spray drying process) under dried state.Particularly desulfurization under wet condition, under dried state, handle the semidry method of desulfurization product, with its advantage that existing wet desulphurization reaction speed is fast, desulfuration efficiency is high, have again that dry method does not have that the sewage spent acid is discharged, an easy-to-handle advantage of desulfurization afterproduct and be subjected to people and pay close attention to widely.In chemical absorbing flue gas desulfurization, the performance of absorbent has fundamentally determined SO
2Absorb the efficient of operation, thereby the performance of absorbent is had very high requirement.Carry out chemical absorbing SO for flue gas
2Process, in order to strengthen mass transport process, improve desulfuration efficiency, reduce investment and the operating cost of equipment, also must possess certain requirement to desulfurizer and operation.
The composite absorber compatibility premium properties of single absorbent, higher mass transfer force, higher absorptive capacity, higher absorption rate and regeneration rate can be provided in absorption process.Therefore composite absorber has higher premium properties, has obtained paying close attention to widely and using in the flue gas desulfurization field.
Film gas absorption techniques (being called for short film absorbs) is separated the new gas separation process that combines with solvent absorption gas technology as film, adopt membrane contactor as desulfurizer, it has stable mass transfer interface, high-specific surface area, high mass transfer efficiency, energy consumption is low, advantages such as device volume is little, and stable operation and elasticity are big; Microporous barrier in the membrane contactor only is the barrier between the gas-liquid two-phase, and to the separation non-selectivity of gas, absorbent provides high selectivity and high drive in separation process.Therefore exploitation and membrane material mutually the high-performance absorbent of compatibility have the meaning of particular importance.At present, be used for membrane contactor and absorb SO
2Composite absorber is less, and absorbent properties also need to improve.We absorb SO at film
2Lot of experiments work has been done in the composite absorber aspect, has proposed the novel and efficient composite absorber, at present at gas cleaning SO
2The field is not seen and is used and report.
Summary of the invention
The object of the present invention is to provide a kind of energy to be used for the sulfur dioxide absorbent that membrane contactor absorbs.
Concrete scheme is as follows:
1, a kind of composite solution for the absorption of film separation sulfur dioxide, the aqueous solution of lactate and amino-acid salt is formed, described lactate is 1:(0.5 ~ 2.2 with the mol ratio of mixing of amino-acid salt).
2, described amino-acid salt is the mixture of any one or two kinds in Beta-alanine salt or the glycinate.
3, described amino-acid salt is sodium salt or sylvite.
4, described lactate is sodium lactate or potassium lactate.
5, described composite solution is the aqueous solution of sodium lactate and Beta-alanine sodium, perhaps be the aqueous solution of sodium lactate and Beta-alanine potassium, perhaps be the aqueous solution of potassium lactate and Beta-alanine sodium, perhaps be the aqueous solution of potassium lactate and Beta-alanine sodium, perhaps be the aqueous solution of sodium lactate and Sodium Glycinate, perhaps being the aqueous solution of sodium lactate and glycine potassium, perhaps is the aqueous solution of potassium lactate and Sodium Glycinate, perhaps is the aqueous solution of potassium lactate and glycine potassium.
6, the total concentration of lactate and amino-acid salt is 0.1 ~ 3.6mol/L in the described composite solution.
7, the total concentration of lactate and amino-acid salt is 0.5～2.8mol/L in the described composite solution.
8, described lactate and amino-acid salt mol ratio are 1:(1～1.6).
The compound desulfurizing agent chemical stability that the present invention proposes is good, and foaminess is little, and viscosity is little, and is nontoxic, and raw material sources are abundant, easily buys low price.The sulfur removal technology of using compound desulfurizing agent disclosed by the invention has high mass tranfer coefficient, and Liquid Flow does not have disturbance, and resistance to mass tranfer is little, the desulfurization degree height, and easy to operate, operating flexibility is big, can stable operation in membrane contactor.The desulfuration solution non-scaling does not stop up simultaneously, does not have corrosion.The compound desulfurizing agent that the present invention proposes can use in membrane contactor, can certainly use in tower class reactor (as bubble tower, packed tower, plate column etc.).
Description of drawings
Fig. 1 absorbs SO for film
2Middle composite solution absorbent properties evaluating apparatus.
Wherein:
1-1-N
2Gas bomb, 1-2-SO
2Gas bomb, 2-gas Quality Control instrument, 3-mixing current stabilization jar, 4-membrane contactor, the 5-measuring pump of wriggling, 6-first solution storage trough, 7-second solution storage trough, 8-infrared gas analyser, P-pressure gauge, A-sample point.
The specific embodiment
Below in conjunction with accompanying drawing the present invention is described in further detail.
Embodiment 1
Be used for the method for evaluating performance that composite solution that the sulfur dioxide film absorbs is used at membrane contactor.
Operating condition: room temperature (19-22 ℃), mixture pressure 0.11MPa, membrane mass transfer area 1.5 m
2, gas flow rate 0.5-2 L/min, flow rate of liquid 200-500mL/min.
As shown in Figure 1, respectively from N
2Gas bomb 1-1 and SO
2The gas of gas bomb 1-2 after gas Quality Control instrument 2 metering, enter mix current stabilization jar 3 form contain the 0.1%-0.6%(percentage by volume) SO
2Gaseous mixture enters in the membrane contactor 4 SO in the gaseous mixture through the gaseous mixture behind the air-flow current stabilization
2Diffuse to the film opposite side by fenestra, absorbed by aforesaid composite solution among the present invention just of compound desulfurizing agent, enter liquid phase, the gas phase after the absorption is emitted from membrane contactor other end gas vent, and the composite absorption solution in the membrane contactor is from first solution storage trough 6.Composite absorption solution is extracted out by wriggling measuring pump 5, and the composite absorption solution in first solution storage trough 6 is sent in the membrane contactor 4, thereby captures the SO that diffusion is come
2Composite solution after the use is discharged from membrane contactor 4, and is stored by second solution storage trough 7.
Gas phase is imported and exported to be made up of infrared gas analyser 8 and is measured.After the sampling of solution component process, by hplc determination, liquid phase SO
2Content adopts spectrophotometry.
Evaluation criterion:
The cumulative volume mass tranfer coefficient
K G a:
SO
2Removal efficiency
η:
In the formula
G,
AWith
LBe respectively gaseous phase volume flow velocity, film cross-sectional area and film length,
C G, inWith
C G, outBe respectively gas phase and import and export SO
2Concentration.
The composite solution that is used for absorption gaseous mixture sulfur dioxide is the aqueous solution of potassium lactate/sodium lactate and glycinate, potassium lactate/sodium lactate and the glycinate total concentration in the aqueous solution is 0.1 ~ 3.6mol/L, and the mol ratio of potassium lactate/sodium lactate and glycinate is 1:(0.5 ~ 2.2).
Glycinate can be the mixture of Sodium Glycinate, glycine potassium or Sodium Glycinate and glycine potassium in the present embodiment.
Adopt the method for evaluating performance among the embodiment 1 to detect.
Process condition: room temperature, gaseous pressure 0.11MPa, gaseous mixture SO
2Content 0.1%-0.6%(percentage by volume), membrane mass transfer area 1.5m
2, gas speed: 0.5-2L/min, liquid speed: 200-500mL/min.
Various desulfurizing agents performance evaluation under various conditions the results are shown in Table shown in 1.
The compound desulfurizing agent performance evaluation of table 1 result
The result shows: composite solution adaptability height disclosed by the invention, not only adapt to low-concentration flue gas, and also adapt to the high concentration flue gas, the concentration of absorbing wide ranges of use, gas-liquid speed operating flexibility is big, SO
2The removal efficiency height, greater than 99%, the film device mass tranfer coefficient is big, between 0.29 ~ 0.42.
The composite solution that is used for absorption gaseous mixture sulfur dioxide is the aqueous solution of potassium lactate/sodium lactate and Beta-alanine salt, potassium lactate/sodium lactate and the total concentration of Beta-alanine salt in the aqueous solution are 0.1 ~ 3.6mol/L, and the mol ratio of potassium lactate/sodium lactate and Beta-alanine salt is 1:(0.5 ~ 2.2).
Beta-alanine salt can be the mixture of Beta-alanine sodium, Beta-alanine potassium or Beta-alanine sodium and Beta-alanine potassium in the present embodiment.
Adopt the method for evaluating performance among the embodiment 1 to detect.
Process condition: room temperature, gaseous pressure 0.11MPa, gaseous mixture SO
2Content 0.1%-0.6%(percentage by volume), membrane mass transfer area 1.5m
2, gas speed: 0.5-2L/min, liquid speed: 200-500mL/min.
Various desulfurizing agents performance evaluation under various conditions the results are shown in Table shown in 2.
The compound desulfurizing agent performance evaluation of table 2 result
The result shows: compound desulfurizing agent adaptability height, not only adapt to low-concentration flue gas, and also adapt to the high concentration flue gas, the concentration of absorbing wide ranges of use, gas-liquid speed operating flexibility is big, SO
2The removal efficiency height, greater than 99%, the film device mass tranfer coefficient is big, at 0.28-0.40.
Claims (8)
1. one kind is used for film and separates the composite solution that sulfur dioxide absorbs, and it is characterized in that described composite solution is made up of the aqueous solution of lactate and amino-acid salt, and described lactate is 1:(0.5 ~ 2.2 with the mol ratio of mixing of amino-acid salt).
2. composite solution according to claim 1 is characterized in that: described amino-acid salt is the mixture of any one or two kinds in Beta-alanine salt or the glycinate.
3. composite solution according to claim 2, it is characterized in that: described amino-acid salt is sodium salt or sylvite.
4. composite solution according to claim 1, it is characterized in that: described lactate is sodium lactate or potassium lactate.
5. composite solution according to claim 2, it is characterized in that: described composite solution is the aqueous solution of sodium lactate and Beta-alanine sodium, perhaps be the aqueous solution of sodium lactate and Beta-alanine potassium, perhaps be the aqueous solution of potassium lactate and Beta-alanine sodium, perhaps be the aqueous solution of potassium lactate and Beta-alanine sodium, perhaps be the aqueous solution of sodium lactate and Sodium Glycinate, perhaps be the aqueous solution of sodium lactate and glycine potassium, perhaps being the aqueous solution of potassium lactate and Sodium Glycinate, perhaps is the aqueous solution of potassium lactate and glycine potassium.
6. according to any described composite solution in the claim 1 to 5, it is characterized in that: the total concentration of lactate and amino-acid salt is 0.1 ~ 3.6mol/L in the described composite solution.
7. composite solution according to claim 6, it is characterized in that: the total concentration of lactate and amino-acid salt is 0.5～2.8mol/L in the described composite solution.
8. composite solution according to claim 1, it is characterized in that: described lactate and amino-acid salt mol ratio are 1:(1～1.6).
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| CN201310284631.6A CN103341301B (en) | 2013-07-09 | 2013-07-09 | A kind of composite solution absorbed for sulfur dioxide in UF membrane |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1759922A (en) * | 2004-10-13 | 2006-04-19 | 中国科学院大连化学物理研究所 | A kind of application of membrane module in mixed gas separation of adopting the densified polymer film |
| WO2012030630A1 (en) * | 2010-09-02 | 2012-03-08 | The Regents Of The University Of California | Method and system for capturing carbon dioxide and/or sulfur dioxide from gas stream |
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2013
- 2013-07-09 CN CN201310284631.6A patent/CN103341301B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1759922A (en) * | 2004-10-13 | 2006-04-19 | 中国科学院大连化学物理研究所 | A kind of application of membrane module in mixed gas separation of adopting the densified polymer film |
| WO2012030630A1 (en) * | 2010-09-02 | 2012-03-08 | The Regents Of The University Of California | Method and system for capturing carbon dioxide and/or sulfur dioxide from gas stream |
Non-Patent Citations (1)
| Title |
|---|
| 常作夫: "关于烧结烟气的脱硫及高空稀释", 《烧结球团》 * |
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