CN101327393A - Equipment and method for processing gas absorbed by film - Google Patents
Equipment and method for processing gas absorbed by film Download PDFInfo
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- CN101327393A CN101327393A CNA2007100576957A CN200710057695A CN101327393A CN 101327393 A CN101327393 A CN 101327393A CN A2007100576957 A CNA2007100576957 A CN A2007100576957A CN 200710057695 A CN200710057695 A CN 200710057695A CN 101327393 A CN101327393 A CN 101327393A
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Abstract
The present invention provides a gas absorption-separation membrane device and a method thereof. Stock solution at a given temperature is contacted with a drainage porous membrane; the absorbed gas under the driving of the blew compressed air or the side sub-pressure of the membrane passes through the porous membrane in gas-status way, and is removed and absorbed for collection at the other side of the membrane. An immersion-typed drainage hollow fiber membrane component is adopted. The compressed air is blown in with an aerated conduit, so as to control the membrane pollution, to obtain the stock solution that is contacted with the membrane and has uniform temperature and concentration, and to provide driving pressure for the air transmission. The membrane leakage problem is resolved by adopting a dual-valve mechanism during the membrane absorption process.
Description
Technical field
The present invention relates to a kind of embrane method GAS ABSORPTION processing method and treating apparatus.
Background technology
In the GAS ABSORPTION field, be a kind of traditional method with air stripping method.The core of tower is sent into and shifted to air from the side, with the ventilation blower that is installed in tower top air discharged from the center of tower then, and this method is simple to operate, reliability height, but energy consumption height, and it is big that equipment takes up an area of volume.
Synthesis ammonia plant is the big volume low-concentration deposed ammonia of by-product in process of production, adopts alkali addition process, makes fixed ammonia resolve into volatilization ammonia again by steam stripping.This technology is simple, and is effective, do not have secondary pollution, and shortcoming is that energy consumption is big, and processing cost is higher.
Although these traditional contact arrangements pillar that always is chemical industry in decades, yet their major defect is that two fluids mix contact fully, therefore the interdependency that has caused two kinds of fluids of contact, and some contact arrangement also can produce phenomenons such as liquid flooding, entrainment, channel, bubbling.
It is a kind of novel chemical separation technology that film separates, and in the last thirty years, the membrane separation technique development has become the important new and high technology and the sustainable development technology that solve the contemporary energy, resource and problem of environmental pollution rapidly.In the GAS ABSORPTION field, develop the integrated separation process of a kind of new membrane-film absorption process with film as the gas-liquid two-phase contact medium, this process brings disaster upon membrane technology and traditional absorption process mutually closes, overcome existingly in traditional absorption process carry secretly, the restriction of operating condition such as liquid flooding.In the film absorption process, gas phase and absorption liquid be in two side flow of film, and carry out mediate contact by the micropore of film, and two phase flow all can be regulated arbitrarily, has enlarged the two-phase opereating specification.
Film absorption process film itself does not have separation function, but it can produce the non-dispersive contact between two immiscible phases and order provides bigger contact area, be a kind of brand-new, effective more contact mass transfer method, thereby make the conventional decentralized photo contactor of this class process have more superiority.In addition, film absorbs and has other some advantages:
Do not require the two alternate density contrasts that exist when (1) being used for the liquid-liquid extraction;
When (2) being used for GAS ABSORPTION, absorbing and be separated in the assembly and finish simultaneously;
(3) be easy to the flexibility of amplifying and handling capacity;
(4) can realize sterile working;
(5) can improve the conversion ratio of some balanced reaction.
The film absorption process can be described with the example that is treated to of ammonia-containing water.As shown in Figure 1, its principle is: hydrophobic microporous membrane is ammonia-containing water and H
2SO
4Absorption liquid is separated in the film both sides, by regulating the pH value of waste water, makes the NH4 of waste water intermediate ion attitude
+Change the volatility NH of molecular state into
3At film both sides NH
3The promotion of concentration difference under, the NH in the waste water
3In the vaporization volatilization of waste water one microporous barrier interface.The NH of gaseous state
3Along the opposite side diffusion of membrane micropore, on absorption liquid one microporous barrier interface, be H to film
2SO
4Absorb, and reaction generates nonvolatile (NH
4)
2SO
4And be recovered.
As mentioned above, ammonia has different existence forms in waste water and absorption liquid: regulating by PH, is the volatility NH with molecular state in waste water
3Form exists, and then is the NH4 with ionic state in absorption liquid
+Form exists.This feature makes conversion that the ammonia in the waste water can be by existence form constantly to the absorption liquid transmission, the H in absorption liquid
2SO
4All be till ammonia neutralizes, thereby can in absorption liquid, obtain the compound of highly concentrated ammonia.
1984, E.L.Cussler proposed the notion of film absorption first and utilizes the hydrophobic polypropylene film to study the gas-liquid mass transfer that is attended by chemical reaction in the hollow fiber film assembly.Measuring NaOH, H
2SO
4Or the aqueous solution of amine is absorbing H
2S, SO
2, NH
3And CO
2Overall mass transfer coefficient in the process found that for the fast response system (as H
2S, SO
2, NH
3), total mass transfer rate only is subjected to the influence of membrane resistance, but for the long response time system (as CO
2), total resistance to mass tranfer is relevant with its resistance to mass tranfer in liquid phase.But,, cause the volume mass transfer rate will improve about 10 times than traditional depassing unit because the loading density in the membrane contactor is higher for all systems.
Over year, this technology has obtained researcher's extensive concern surplus in the of 20.As utilize the polypropylene hollow fiber membrane assembly carried out ammonia/moisture from the various researchs that influence separating effect because of rope, select for use sulfuric acid as absorption liquid, ammoniacal liquor pumps into the hollow-fibre membrane inboard, sour absorption liquid circulates in the film outside.The result shows: the mass tranfer coefficient in the separation process depends primarily on raw materials ammonia one side, it is directly proportional with three/first power of material liquid flow velocity, and irrelevant with inlet pressure that absorbs acid strength, material liquid and concentration, in all process conditions, temperature is the most remarkable to the influence of mass transport process; The increase of ammonia flow rate, mass tranfer coefficient increases and the removal efficiency decline of ammonia; The concentration of ammonia, the concentration of sour absorption liquid, flow velocity influence less to mass transport process.The membrane absorption method deamination rate of making absorption liquid with sulfuric acid is greater than 99.9%, and can reclaim the sulfate of ammoniac of higher degree; And make absorbent with the hydrochloric acid of high concentration (concentration is greater than 8%), owing to the volatility of hydrochloric acid, in fenestra, generate the sal-ammoniac crystal easily, thereby cause the hydrophiling trend of hydrophobic microporous membrane.
Solute separates mass transport process and mainly is made up of three steps, as shown in Figure 2.Fig. 2 is a hydrophobic porous film GAS ABSORPTION mechanism of mass transfer schematic diagram, among the figure, and P
AExpression body gas component A dividing potential drop; P
Am: expression film gas phase side component A dividing potential drop, P
AiExpression film liquid side gas component dividing potential drop; C
A: expression liquid phase main body concentration; C
AiExpression and gas phase P
AiConcentration of component in the liquid phase of one-tenth balance.In Fig. 2, solute by raw material phase main diffusion to membranous wall; Be diffused into the film opposite side by membrane micropore again; Be diffused into by the opposite side membranous wall and accept the phase main body.In the separation process that has chemical reaction to exist, different is after absorbent is diffused into the interface that contacts, and with certain the component generation chemical reaction in absorbent or the absorbent, reacted product or partial reaction thing and product are together to the absorbent main diffusion.For desorption process, the mass transfer direction is opposite.Total resistance to mass tranfer comprises feed liquid phase resistance, membrane resistance with accept resistance mutually.
Film absorbs application study to be realized traditional absorption process with membrane process, the advantage that film embodied is mainly in phase-splitting with relatively large phase-contact surface is provided.The film absorption process is failed the main bottleneck of large-scale industrial application and is come from membrane material itself,
There are several problems in actual applications in present film absorption process:
(1) introducing of film has increased the resistance to mass tranfer of system, particularly when fenestra topping up body;
(2) inhomogeneities of shell-side fluid distribution influences mass-transfer efficiency;
(3) film pollutes exists (though little than the pressure-driven membrane process);
(4) life-span of film;
(5) long-time running makes the hydrophiling tendency of hydrophobic membrane;
(6) problem of critical breakthrough pressure.
Fig. 3 has shown conventional film modular construction schematic diagram.As shown in Figure 3, tube side fluid enters membrane module from tube side fluid import 33, flows out from tube side fluid outlet 36, and shell-side fluid enters membrane module from shell-side fluid import 35, flows out membrane module from shell-side fluid outlet 34.Be provided with doughnut 31 and fluid sealant 32 in the membrane module.
The feature of " concurrent flow " assembly be tube side and shell side fluid with and the stream or the form PARALLEL FLOW of adverse current.The outstanding advantage of this kit form is that manufacturing process is simple, and cost is lower, so it also is industrial the most frequently used.But because normally inhomogeneous filling of fiber in the concurrent flow assembly, this causes the uneven distribution of shell-side fluid easily, and then influence mass-transfer efficiency.
In the operating process that film absorbs, keep certain pressure reduction to form stable mass transfer interface between the gas-liquid two-phase, two alternate pressure reduction only are to prevent two alternate infiltrations, the main motive force of film absorption process is that two alternate activity are poor, rather than two alternate pressure reduction, pressure reduction is far smaller than the contribution of activity difference to chemical potential difference to the contribution of chemical potential difference, so the mass tranfer coefficient of film absorption process is not subjected to the influence of two-phase pressure reduction substantially, this be that the motive force Membrane Gas Separation Processes is different with pressure reduction.
Summary of the invention
The objective of the invention is to overcome defective of the prior art, a kind of device and method of gas absorption separation is provided.
Obtain following effect by the present invention:
1, mechanism of mass transfer is a pressure differential, and negative pressure suction or malleation compressed air purge, and mass-transfer efficiency improves.
2, bivalve effusion separating mechanism has solved the film leakage problems of hydrophobic membrane in the middle of using of long-term puzzlement.
3, the immersion hydrophobic membrane filter assemblies that has aeration tube, it is big to need not that stoste is carried out complicated pre-filtering processing, film contact area.Stir by the aeration tube air-blowing, make processed liquid and hydrophobic membrane silk even contact in the reaction tank, reduce concentration polarization and temperature difference polarization, simultaneously, utilize bubble friction swing effect, controlling diaphragm pollutes.
Description of drawings
Fig. 1 is a film principle of absorption schematic diagram in the prior art;
Fig. 2 is a hydrophobic porous film GAS ABSORPTION mechanism of mass transfer schematic diagram;
Fig. 3 is a conventional film modular construction schematic diagram;
Fig. 4 is a film absorption plant schematic diagram of the present invention;
Fig. 5 A is a membrane module film silk inverted U cast structure schematic diagram of the present invention;
Fig. 5 B is a membrane module film silk U type cast structure schematic diagram of the present invention;
Fig. 5 C is the straight type of membrane module film silk of the present invention two ends cast structure schematic diagrames;
Fig. 6 is a bivalve output mechanism schematic diagram in the film absorption plant of the present invention.
The specific embodiment
As Fig. 4, film absorption plant of the present invention comprises: reaction tank 2, be arranged on liquor inlet 1, air intake 9 on the reaction tank 2, be arranged on the hydrophobic hollow-fibre membrane gas-liquid separator 3 of immersion in the reaction tank 2, be arranged on the boring aeration pipe 4 of the controlling diaphragm pollution of separator 3 bottoms, be arranged on the absorption liquid container 5 of reaction tank outside, negative pressure pump 6 is set in absorption liquid container outlet 5 back, it adopts the negative pressure suction, will be absorbed in the gas importing absorption liquid container 5 to absorb collection.Perhaps, blast compressed air, will be absorbed gas purging and see through film, enter in the absorption liquid container 5 and absorb collection by boring aeration pipe 4.When compressed air purges, do not need negative pressure pump 6 in the device.
Solid content is then discharged the film absorption plant from low level outlet 7 in the reaction tank 2.
Negative pressure pump 6 can be a vavuum pump, also can be the negative pressure that produces when utilizing water pump to carry fluid.
Film in the gas-liquid separator 3 is a Kynoar doughnut hydrophobic membrane, internal diameter: 0.2-3.0mm, and wall thickness: 0.05-1.0mm, many of film evaporators are formed one-level side by side, and multi-stage series connection constitutes one group.
Be provided with air aeration pipe 4 in the reaction tank 2, it has three effects: the one, stir by air-blowing, and make processed liquid and hydrophobic membrane silk even contact in the reaction tank 2, reduce concentration polarization and temperature difference polarization; The 2nd, utilize bubble friction swing effect, controlling diaphragm pollutes; The 3rd, utilize the air supporting castering action, make the suspension come-up, overflow evaporimeter from come-up pollutant emission mouth 8, or under reaction tank 2 closed states, blast malleation compressed air, will be absorbed gas and take reactant liquor out of by film, enter absorption liquid.
When solid content impurity content in reaction tank 2 stops aeration more for a long time, make solid content under the gravity effect, sink naturally, discharge from low level outlet 7.
The membrane module structure form of hydrophobic membrane can be for U type, inverted U, straight type, shown in Fig. 5 A-5B.Fig. 5 A is a membrane module film silk inverted U cast structure schematic diagram of the present invention; Fig. 5 B is a membrane module film silk U type cast structure schematic diagram of the present invention; Fig. 5 C is the straight type of membrane module film silk of the present invention two ends cast structure schematic diagrames.
Because the air permeability of hydrophobic membrane is good, for controlling diaphragm pollutes, can feed low-pressure compressed air from air intake 9, carry out pressing in the air impact of backlashes to clean to film.
Can adopt hydrophobic film materials such as Kynoar, polypropylene, polyethylene as gas-liquid separation, the membrane structure form can adopt hollow-fibre membrane, flat sheet membrane, tubular membrane component, and the preferred Kynoar hollow fiber film assembly of the present invention is as gas-liquid separator.According to the difference for the treatment of capacity, can in parallel or series connection use simultaneously with a plurality of membrane modules.
The present invention has designed new film absorption process, the reaction stoste that will have uniform temperature contacts with hydrophobic porous film, absorbed gas sees through under the driving of side negative pressure at compressed air that blasts or film, passes perforated membrane in the gaseous state mode, enters the absorption liquid container and is absorbed collection.The effusion that sees through film is then discharged the film absorption plant by bivalve shown in Figure 6.Fig. 6 has shown the drainage mechanism 10 among Fig. 4.As shown in Figure 6, be absorbed the low level of gas piping, be connected with bivalve drainage mechanism 10.Above-mentioned bivalve drainage mechanism 10 comprises upper valve 11 and bottom valve 13.During equipment work, valve 11 is often opened, and valve 13 is normally closed, like this, because what the seepage of hydrophobic membrane produced directly sees through liquid because the effect of gravity enters in the container 12 automatically, when having a certain amount of effusion in the container 12, valve-off 11, open valve 13, effusion in the container 12 is discharged system, and then, valve-off 13 once more, open valve 11, collect the effusion of hydrophobic membrane.
Characteristics of the present invention are:
1, mechanism of mass transfer is a pressure differential
Film absorbed mechanism of mass transfer for utilizing the partial pressure difference that is absorbed gas in the past, belonged to gas molecule diffusion mechanism, and mechanism of the present invention is pressure differential, and pressure reduction can be positive differential pressure or Negative Pressure Difference.Advantage: gas flow rates is higher than the natural diffusion velocity of solute under partial pressure difference under the pressure-driven, and mass-transfer efficiency improves.
2, the bivalve effusion separates
Adopt the bivalve output mechanism, solved the film leakage problems of hydrophobic membrane in the middle of using of long-term puzzlement.
3, the immersion hydrophobic membrane filter assemblies that has aeration tube
Usually to absorb be to adopt the inner pressed hollow-fibre membrane to film, and the stoste hollow-fibre membrane inboard of flowing through because the hollow-fibre membrane internal diameter is little, makes the hollow fiber film tube inner flow passage stop up easily, therefore former water pretreatment is required high.The present invention adopts immersion external pressure doughnut hydrophobic membrane as gas-liquid separator, and external pressure doughnut hydrophobic membrane directly is immersed in the stoste reaction tank, and advantage is that to need not that stoste is carried out complicated pre-filtering processing, film contact area big.Usually the film absorption is to adopt column-type film components, the present invention adopts the submergence integral type, on the one hand, facility compact, simple in structure, on the other hand, effectively controlling diaphragm pollutes, and easy cleaning (can adopt the good air of easy control and cleaning performance to clean), is difficult at the film surface scale, and pollutant utilizes easily that gravity sinks to collecting naturally, suspended impurity utilizes the discharge of floating of air supporting castering action easily.Air aeration Guan Yousan effect: the one, stir by air-blowing, make processed liquid and hydrophobic membrane silk even contact in the reaction tank 2, reduce concentration polarization and temperature difference polarization; The 2nd, utilize bubble friction swing effect, controlling diaphragm pollutes; The 3rd, utilize the air supporting castering action, make the suspension come-up, overflow evaporimeter from exporting 8, or under reaction tank 2 closed states, blast malleation compressed air, will be absorbed gas and take reactant liquor out of by film, enter absorption liquid.
Usually the film absorption is to adopt column-type film components, the present invention adopts the submergence integral type, on the one hand, facility compact, simple in structure, on the other hand, effectively controlling diaphragm pollutes, and easy cleaning (can adopt the good air of easy control and cleaning performance to clean), is difficult at the film surface scale, and pollutant utilizes easily that gravity sinks to collecting naturally, suspended impurity utilizes the discharge of floating of air supporting castering action easily.
System of the present invention is applicable to that the chemical industry volatile material separates.
Reclaim as ammoniacal liquor, after containing ammonia solution and adding the alkali ammonification, blast compressed air, compressed air under pressure-driven, sees through the hydrophobicity diffusion barrier with ammonia, enters acid solution again and absorbs.
Reclaim as ammoniacal liquor, after containing ammonia solution and adding the alkali ammonification, film see through the suction of side negative pressure, under pressure-driven, see through the hydrophobicity diffusion barrier, enter acid solution again and absorb.
Extract to reclaim as bromine, after containing bromine solutions and adding sour bromination, blast compressed air, compressed air under pressure-driven, sees through the hydrophobicity diffusion barrier with bromine gas, enters alkali lye again and absorbs.
Extract to reclaim as bromine, after containing bromine solutions and adding sour bromination, film see through the suction of side negative pressure, under pressure-driven, see through the hydrophobicity diffusion barrier, enter alkali lye again and absorb.
Claims (10)
1, a kind of gas absorbed by film treating apparatus is characterized in that, comprising:
Reaction tank (2);
Be arranged on the liquor inlet (1) on the reaction tank (2);
Be arranged on the immersion hydrophobic membrane gas-liquid separator (3) in the reaction tank (2), carry out gas-liquid separation;
Be arranged on the boring aeration pipe (4) of separator (3) bottom;
Be arranged on the absorption liquid container (5) of reaction tank outside, gas is collected.
2, gas absorbed by film treating apparatus according to claim 1 is characterized in that:
Be provided with negative pressure pump (6) in absorption liquid container outlet (5) back.
3, gas absorbed by film treating apparatus according to claim 1 is characterized in that:
On reaction tank (2), also be provided with compressed air inlet (9), be used for that film is carried out air and impact cleaning.
4, gas absorbed by film treating apparatus according to claim 1 is characterized in that:
Film in the gas-liquid separator (3) is a Kynoar doughnut hydrophobic membrane, internal diameter: 0.2-3.0mm, and wall thickness: 0.05-1.0mm, many of film evaporators are formed one-level side by side, and multi-stage series connection constitutes one group.
5, gas absorbed by film treating apparatus according to claim 1 is characterized in that:
Reaction tank (2) top is provided with floating pollutant emission mouth (8), utilizes boring aeration pipe (4) emission gases air supporting castering action, makes the suspension come-up and overflows evaporimeter from come-up pollutant emission mouth (8);
Reaction tank (2) bottom is provided with low level outlet (7), and solid content is then discharged the film absorption plant from low level outlet (7) in the reaction tank (2).
6, gas absorbed by film treating apparatus according to claim 1 is characterized in that:
Be absorbed the low level of gas piping, be connected with bivalve drainage mechanism (10);
Above-mentioned bivalve drainage mechanism (10) comprises upper valve (11) and bottom valve (13), and is arranged on the container (12) between the valve of top and the bottom;
During equipment work, upper valve (11) is often opened, and bottom valve (13) is normally closed, because the direct of the seepage of hydrophobic membrane generation sees through liquid because the effect of gravity enters in the container (12) automatically, when having a certain amount of effusion in the container (12), valve-off (11) is opened valve (13), and the effusion in the container (12) is discharged system, then, valve-off (13) is opened valve (11) once more, collects the effusion of hydrophobic membrane.
7, a kind of gas absorbed by film processing method is characterized in that:
The stoste that will have uniform temperature is discharged in the reaction tank (2) from liquor inlet (1), and it is contacted with hydrophobic porous film in the submerged membrane gas-liquid separator (3);
Be absorbed gas seeing through under the driving of side negative pressure, pass perforated membrane, be removed and absorb collection at the opposite side of film in the gaseous state mode by the compressed air that blasts or film.
8, according to the described gas absorbed by film processing method of claim 7, it is characterized in that:
The employing negative pressure is aspirated, and will be absorbed in the gas importing absorption liquid container (5) to absorb collection.
9, according to the described gas absorbed by film processing method of claim 7, it is characterized in that:
Blast compressed air by boring aeration pipe (4), will be absorbed gas purging and see through film, enter in the absorption liquid container (5) and absorb collection.
10, according to the described gas absorbed by film processing method of claim 7, it is characterized in that:
By blasting compressed-air actuated mode, controlling diaphragm pollutes, makes former liquid temp that the film wire connection touches even and provide driving pressure for gas transfer with concentration.
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| CNA2007100576957A CN101327393A (en) | 2007-06-20 | 2007-06-20 | Equipment and method for processing gas absorbed by film |
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|---|---|---|---|
| CNA2007100576957A CN101327393A (en) | 2007-06-20 | 2007-06-20 | Equipment and method for processing gas absorbed by film |
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| CN103877828A (en) * | 2012-12-21 | 2014-06-25 | 中国科学院大连化学物理研究所 | Absorption liquid regeneration method and special-purpose absorption liquid regeneration device |
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