A kind of method and system for the admixture of gas depickling containing sour gasThe application is Chinese invention patent application (denomination of invention：It is a kind of to be taken off for the admixture of gas containing sour gasThe method and system of acid；Application number：201310487939.0；The applying date：On October 17th, 2013) divisional application.
Technical field
The present invention relates to a kind of deacidifying process of effective admixture of gas, absorbent is used more particularly, to one kindThe method concentrated again after sour gas is absorbed, sour gas is separated from admixture of gas, the technique can increase acidityThe absorption rate that gas separates from admixture of gas, and reduce the total energy consumption for depickling operation.
Background technology
Many production technologies need to remove sour gas from admixture of gas, for example, initial natural gas or other bagsThe depickling of the admixture of gas of a large amount of sour gas is included, described sour gas includes hydrogen sulfide (H2S), carbon dioxide (CO2)Or similar contaminant matter.Acid gas impurities in admixture of gas are reduced to acceptable level by deacidifying process.The stepSuddenly generally completed by amine handling process, the amine handling process is relatively conventional in various types of industrial productions, such as refines oilFactory, gas plant and chemical plant.Amine handling process using amine the aqueous solution remove sour gas (such as hydrogen sulfide andCarbon dioxide) technique.
Common deacidifying process is solution-air absorption technique, and typical solution-air absorption technique is generally included containing being intended to removeThe admixture of gas of sour gas contacted with liquid amine aqueous solution, by amine aqueous solution as the absorbent for absorbing sour gas.In industrial production, the amine that most generally uses is hydramine, such as monoethanolamine (MEA) and diethanol amine (DEA).Recently, by methylDiethanol amine (MDEA) is separated into industrial production application of interest for carbon dioxide (CO2).At present, diisopropanolamine (DIPA)(DIPA) it is used for sulfone amine method technology and SCOT techniques, it is net that the SCOT techniques are used for Crouse (Claus) device acid tail gasChange.
In typical solution-air absorption technique, after sour gas is inhaled into the absorbent in absorptive unit, rich gas is inhaledReceive agent and be admitted to regeneration unit, in the regeneration unit, rich gas absorbent regenerates to be divided into and absorbed after processing and separationGas and lean gas absorbent.Then, the lean gas absorbent of the regeneration is cycled back into absorptive unit, and according to userPurpose, by sour gas collect or discharge.In the solution-air of this type absorbs, the energy consumption of the regeneration technology accounts for total energyLoss-rate weighs more than 80%, because whole absorbents must be regenerated, to be reused in absorptive unit.In addition, the allusion quotationThe solution-air absorption technique of type is limited to a kind of liquid form and uses a kind of absorbent.
The content of the invention
The present invention relates to a kind of deacidifying process of effective admixture of gas, absorbent is used more particularly, to one kindAbsorb the method concentrated again after sour gas to separate sour gas from admixture of gas, the technique can increase sour gasThe absorption rate that body separates from admixture of gas, and reduce the total energy consumption for depickling operation.
The technical scheme is that a kind of method for the admixture of gas depickling containing sour gas, the sideMethod includes：
A, acid gas mixture is contacted with the absorbent in absorptive unit, the absorbent is dissolved with initial concentrationA kind of material in a solvent, one or more of the material in following composition：Amine, amino-acid salt, acid amides,Alkali, alkali salt, alkaline earth salt, ammonium salt, urea, alkali metal phosphonate, carbonate, borate, acid phosphite, phosphite,Phosphonite, hypophosphites, phosphonate, superphosphate, pyrophosphite, bicarbonate, metaborate, biborate,Tetraborate, pentaborate；
B, make the absorbent absorb sour gas and form rich gas absorbent；
C, the rich gas absorbent is made to concentrate to form condensed matter phase；
D, the condensed matter is made mutually to be separated from the remainder of the absorbent；The condensed matter mutually includes concentrationCondensed matter and absorbed sour gas higher than initial concentration, wherein condensed matter include material or its chemical modification(the agent having chemical modification), absorbed sour gas include sour gas or its changeLearn modifier (the acid gas having chemical modification)；
E, the remainder of the absorbent is cycled back into absorptive unit；
F, the condensed matter is mutually delivered into regeneration unit, to obtain sour gas and the condensed matter；Also,
G, the condensed matter by regeneration is cycled back into absorptive unit.
The initial concentration of above-mentioned substance is 0.001-99.9wt%.
In a preferred embodiment, methods described includes：
A, acid gas mixture is contacted with the absorbent in absorptive unit, the absorbent is dissolved with initial concentrationAmine in a solvent；The initial concentration of the amine is 0.001-99.9wt%；
B, make the absorbent absorb sour gas and form rich gas absorbent；
C, rich gas absorbent is made to concentrate to form concentration amine phase；
D, the concentration amine is made mutually to be separated from the remainder of the absorbent；The concentration amine is mutually higher than comprising concentrationThe concentration amine and absorbed sour gas of initial concentration, wherein concentration amine includes amine or its chemical modification (the amineHaving chemical modification), absorbed sour gas includes sour gas or its chemical modification(the acid gas having chemical modification)；
E, the remainder of the absorbent is cycled back into absorptive unit；
F, the concentration amine is mutually delivered into regeneration unit, to obtain sour gas and the concentration amine；Also,
G, the concentration amine by regeneration is cycled back into absorptive unit.
Further, one or more of the sour gas in following gaseous matter：Carbon dioxide(CO2), sulfur dioxide (SO2), sulfur trioxide (SO3), hydrogen sulfide (H2S), carbonyl sulfide (COS), carbon disulfide (CS2), mercaptan(RSH), nitric oxide (NO), nitrogen dioxide (NO2), fluoride, hydrochloric acid.
Preferably, the amine in the above method is selected from the one or more of following material：Organic amine, MEA,Diethanol amine, triethanolamine, monoethanolamine, isopropanolamine, ethylene amines, alkyl-alkanolamine, methyl diethanolamine, piperidines, twoButylamine, diisopropylamine；
Preferably, the solvent is selected from one kind of following component：Water, amine, amino acid, amino-acid salt, acid amides, alcohol, secondGlycol, mercaptan, phenol, alkane, unsaturated hydrocarbon, ether, ester, aldehyde, ketone, carboxylic acid, phosphonic acids, glycol ether, carbonic acid Asia hydrocarbonEster, carbonic diester, sulfolane, ionic liquid, polymer, organic silicon solvent, organic fluorous solvent；Or include one or more saltAnd/or the organic solution of the aqueous solution of alkali, one or more salt and/or alkali, the salt are selected from following group：Alkali, alkali salt,Alkaline earth salt, ammonium salt, urea, alkali metal phosphonate, alkanolamine, alkaline earth salt, phosphate, acid phosphite, phosphite,Phosphonite, hypophosphites, phosphonate, superphosphate, pyrophosphite, carbonate, bicarbonate, borate, inclined boronHydrochlorate, biborate, tetraborate and pentaborate, and the derivative of the various salt.
Compared to the absorption rate that sour gas is individually absorbed by amine, the solvent can increase sour gas suction absorbentInterior absorption rate.
Further, one or more of the amine in including following material：MEA, diethanol amine,Piperidines, dibutyl amine, or diisopropylamine, triethanolamine, monoethanolamine, isopropanolamine, ethylene amines, alkyl-alkanolamine and methylDiethanol amine；The solvent includes at least one of following material：Water, alcohol, ethylene glycol, glycol ether, the silica of decamethyl fourAlkane and the siloxen of decamethyl four, gallic acid, PZ, benzoquinones, carbohydrazide, piperazine, Yi ZhonghuoThe aqueous solution of a variety of salt and/or alkali, the organic solution of one or more salt and/or alkali, the alkali and salt include hydroxideSodium, potassium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, sodium acid carbonate, saleratus.
The absorption of the step a, step c concentration and step d separation can occur non-concurrent to occur simultaneously.
The absorption of the step a, step c concentration and step d separation can occur in same unit, can also beOccur in different units.
In a preferred embodiment, the method for concentration includes phase conversion method (Phase TransitionalMethod), phase change method (Phase Change Method), method of evaporating, gasification process, method for crystallising, UF membrane sideMethod, pervaporation, extraction, filter method, method for concentration also include passing through temperature change, pressure change, change in concentration, solubilityThe caused concentrate process of change, and any equipment of concentration can be provided..
The method according to the invention, it is preferred that the absorptive unit is an absorber, a membrane contactor and energyAny equipment of air-liquid contact is enough provided.
In one embodiment, including a kind of renovation process, the renovation process are selected from the group formed by the following method：Thermal decomposition method, air- extraction, vaporizing extract process, vacuum method, the way of distillation, handled by membrane contactor, pervaporation method, pressure differential method,Microwave method, including by temperature change, pressure change, reach regeneration method, and the combination of above method.
Further, the renovation process be selected from thermal decomposition method, air- extraction, vaporizing extract process, vacuum method, the way of distillation and more thanThe combination of method.
In a preferred embodiment, the concentration of the concentration amine before the concentration amine mutually regenerates is more than 50wt%. againWhen raw, the concentration for concentrating amine is the higher the better.It is described to concentrate the concentration amine before amine mutually regenerates in a further preferred embodimentConcentration be 88wt%-100wt%.
In another preferred embodiment, the concentration of the condensed matter before the condensed matter mutually regenerates is more thanIn a more preferred embodiment, the concentration of condensed matter before the condensed matter mutually regenerates is 88wt%- to 50wt%.100wt%.
Present invention also offers a kind of system for the admixture of gas depickling containing sour gas, the system bagInclude：
Absorptive unit, the absorptive unit be used for admixture of gas is in contact with absorbent, the absorbent comprising withThe amine of initial concentration dissolving in a solvent, the absorbent absorb sour gas and form rich gas absorbent, the rich gas absorbentConcentration forms concentration amine phase, and the concentration amine mutually separates from the remainder of the absorbent concentrates amine mutually comprising dense described inConcentration amine of the degree higher than initial concentration and absorbed sour gas, wherein concentration amine includes amine or its chemical modification (theAmine having chemical modification), absorbed sour gas includes sour gas or its chemistry changesProperty thing (the acid gas having chemical modification)；
Upgrading unit, the upgrading unit are used to concentrate in the rich gas absorbent to form concentration amine phase；
Separative element, the separative element are used to mutually separate the concentration amine from the remainder of the absorbent；With
Regeneration unit, the regeneration unit is used for the regeneration of the concentration amine phase, to obtain the sour gas and concentrationAmine.
Still further aspect, of the invention further relates to a kind of system for the admixture of gas depickling containing sour gas,The system includes：
Absorptive unit, the absorptive unit are used to make admixture of gas be in contact with absorbent, and the absorbent contains moltenA kind of material of the solution in the solvent of initial concentration, the material are selected from the one or more of following composition：Amine, amino acidSalt, acid amides, alkali, alkali salt, alkaline earth salt, ammonium salt, urea, alkali metal phosphonate, carbonate, borate, acid phosphite, phosphorousHydrochlorate, phosphonite, hypophosphites, phosphonate, superphosphate, pyrophosphite, bicarbonate, metaborate, two boronHydrochlorate, tetraborate, pentaborate；
The absorbent absorbs sour gas and forms rich gas absorbent, and the rich gas absorbent concentrates to form condensed matterPhase, the condensed matter mutually separate condensed matter described in mutually comprising concentration higher than initial from the remainder of the absorbentThe condensed matter of concentration and absorbed sour gas, wherein condensed matter include material or its chemical modification (theAgent having chemical modification), absorbed sour gas includes sour gas or its chemistry changesProperty thing (the acid gas having chemical modification)；
Upgrading unit, the upgrading unit are used to concentrate to form condensed matter phase by the rich gas absorbent；
Separative element, the separative element are used to mutually separate condensed matter from residual absorption agent；And
Regeneration unit, the regeneration unit is used for the regeneration of material concentration phase, to obtain the sour gas and instituteState condensed matter.
In above-mentioned two system, the one kind of the solvent in including following material：Water, amine, amino acid, amino acidSalt, acid amides, alcohol, ethylene glycol, mercaptan, phenol, alkane, unsaturated hydrocarbon, ether, ester, aldehyde, ketone, carboxylic acid, phosphonic acids, second twoAlcohol ether, alkylene carbonate, carbonic diester, sulfolane, ionic liquid, polymer, organic silicon solvent, organic fluorous solvent；Or bagThe organic solution of the aqueous solution containing one or more salt and/or alkali, one or more salt and/or alkali, the salt are selected from such asUnder group：Alkali, alkali salt, alkaline earth salt, ammonium salt, urea, alkali metal phosphonate, alkanolamine, alkaline earth salt, phosphate, acid phosphorousHydrochlorate, phosphite, phosphonite, hypophosphites, phosphonate, superphosphate, pyrophosphite, carbonate, bicarbonateSalt, borate, metaborate, biborate, tetraborate and pentaborate, and the derivative of the salt.
The beneficial effects of the invention are as follows：The method that concentrates again is absorbed after sour gas by sour gas from gas using absorbentSeparated in body mixture, the technique can increase the absorption rate for separating sour gas from admixture of gas, and reduce useIn the total energy consumption of depickling operation.
Only concentrating mutually needs to regenerate, and so as to reduce solvent circulation, reduces regeneration institute calorific requirement, reduces to circulating coolingThe demand of water, so as to substantially reduce the total energy consumption of whole deacidification.
Other aspects of the present invention, feature and advantage will pass through following detailed description of the present invention, preferable implementationScheme and appended claims are fully disclosed.
Brief description of the drawings
The above and described further below that the present invention may be better understood is read in conjunction with the figure.For illustrating thisThe purpose of invention, picture shown for the preferred embodiments of the present invention.It should be understood, however, that the present invention is not limited in pictureShown layout and means.
The flow chart for the step of Fig. 1 is the deacidifying process shown in foundation one embodiment of the invention.
Embodiment
Unless otherwise defined, it is related to the present invention, general with this area with all science and technology here and scientific terminologyLogical technical staff's has been generally understood that identical implication.Otherwise, the implication of some terms used herein has this specification instituteThe implication of setting.All patents cited herein, disclosed patent application and publication have been incorporated by reference into textIn, as illustrate here comprehensively.It should be noted that unless context explicitly indicate that state otherwise it is outer, for hereinSingulative especially in appended claims includes plural reference.
On the one hand, the present invention relates to a kind of deacidifying process of effective admixture of gas, used more particularly, to one kindThe method that concentrates again separates sour gas from admixture of gas after absorbent absorbs sour gas, the technique can increase byThe absorption rate that sour gas separates from admixture of gas, and reduce the total energy consumption for depickling operation.
According to one embodiment of the invention, absorbent and the admixture of gas including the sour gas to be removed is oneContacted in individual absorptive unit.The absorbent is included with a kind of initial concentration dissolving amine in a solvent or a kind of material.InhalingDuring receipts, either the material concentration turns into concentration amine phase or the concentration phase of the material to the amine in absorbent.Can alsoAfter completion is absorbed, by the amine in absorbent, either the material is concentrated as the concentration of amine phase or the material is concentratedPhase.The concentration of the concentration amine phase or the material is mutually separated from the remainder of absorbent.The initial concentration of the amineFor 0.001-99.9wt%, the initial concentration of the material is also 0.001-99.9wt%.Preferably, the initial concentration of amine is1-90wt%.It is further preferred that the initial concentration of amine is preferably for 3-80wt%., the initial concentration of above-mentioned substance is 1-90wt%.Do not have it is further preferred that the initial concentration of above-mentioned substance is 3-80wt%. to the material in absorbent or the concentration of amineThere are special requirement, it is different adjustable according to the content of sour gas.
The sour gas to be removed, for example, it may be one or more sour gas, the sour gas is selected from such asUnder group：Carbon dioxide (CO2), sulfur dioxide (SO2), sulfur trioxide (SO3), hydrogen sulfide (H2S), carbonyl sulfide (COS), twoNitric sulfid (CS2), mercaptan (RSH), nitric oxide (NO), nitrogen dioxide (NO2), fluoride, hydrochloric acid, and combinations thereof.
According to the absorptive unit in embodiment of the present invention, can be absorption tower either membrane contactor or otherThe solution-air osculating element that technical field technical staff knows.
Those skilled in the art of the present technique readily appreciate, and the absorbent may include that one or more are dissolved in a kind of solventAmine.The example of the amine includes but is not limited to MEA, diethanol amine, triethanolamine, monoethanolamine, isopropanolamine, sub- secondBase amine, alkyl-alkanolamine, methyl diethanolamine, piperidines, dibutyl amine, diisopropylamine, and its derivative or mixture.
The solvent can be aqueous solvent or organic solvent.For example, the aqueous solvent can be water, one or more saltThe aqueous solution, the aqueous solution of one or more alkali.The organic solvent can be organic solvent, one or more salt it is organic moltenLiquid, the organic solution of one or more alkali, the water of one or more salt and the mixed solution of organic solvent, one or more alkaliThe mixed solution of water and organic solvent, the salt include but is not limited to alkali salt, alkaline earth salt, ammonium salt, urea, alkali metal phosphonate,Alkanolamine, alkaline earth salt, phosphate, acid phosphite, phosphite, phosphonite, hypophosphites, phosphonate, acidityPhosphate, pyrophosphite, carbonate, bicarbonate, borate, metaborate, biborate, tetraborate and five boric acidSalt, and its derivative.The organic solvent may include one or more components, the component include but is not limited to amine, amino acid,Amino-acid salt, acid amides, alcohol, ethylene glycol, mercaptan, phenol, alkane, unsaturated hydrocarbon, ether, ester, aldehyde, ketone, carboxylic acid, phosphineAcid, glycol ether, alkylene carbonate, carbonic diester, sulfolane, ionic liquid, polymer, organic silicon solvent, organic fluorous solvent,And its derivative.Further, the solvent can be a kind of aqueous solution and a kind of composition of organic solvent.
The amine also be can dissolve and/or be mixed in other one or more amine, other one or more material, for example,Amino acid, amino-acid salt, acid amides, alkali, alkali salt, alkaline earth salt, ammonium salt, urea, alkali metal phosphate, carbonate, borate, acidityPhosphite, phosphite, phosphonite, hypophosphites, phosphonate, superphosphate, pyrophosphite, bicarbonate,Metaborate, biborate, tetraborate, pentaborate.
In a preferred embodiment, the solvent includes ethylene glycol, glycol ether, C5 to C12 alcohol, decamethylTetrasiloxane (decamethyltetrasiloxane) or the siloxen of decamethyl four (decamethyltetrasiloxine)More than two kinds of composition in the solution of water/organic solvent of the solution of water/organic solvent of alkali, carbonic acid and bicarbonate.
The solvent also can be the solvent for being insoluble or slightly soluble in water, such as alcohol not soluble in water, ethylene glycol, second twoAlcohol ether, organic silicon solvent or organic fluorous solvent.Further, the solvent can be ionic liquid or polymer.
The solvent also can be the aqueous solution of water, the aqueous solution of alkali, carbonic acid and bicarbonate.
In one embodiment of the invention, the absorbent includes the amine being dissolved in solvent, and the solvent includesBut it is not limited to alcohol, ethylene glycol, glycol ether, organic silicon solvent, organic fluorous solvent, monoethanolamine solution, diethanol amine, three ethanolAmine, monoethanolamine, isopropanolamine, ethylene amines, alkyl-alkanolamine (alkyl alkanolamines), methyl diethanolamine,Piperidines, dibutyl amine, diisopropylamine, mercaptan, phenol, carboxylic acid, water, the aqueous solution of alkali, the organic solution of alkali, carbonic acid and bicarbonateThe aqueous solution, the organic solution of carbonic acid and bicarbonate, its derivative or mixture.
In one embodiment of the invention, the amine can be substituted with other materials.For example, the amine substitute materials can be withIt is amino acid, amino-acid salt, acid amides, alkali, alkali salt, alkaline earth salt, ammonium salt, urea, alkali metal phosphonate, carbonate, borate, acidProperty phosphite, phosphite, phosphorous acid derivative (phosphonite), hypophosphites, phosphonate, superphosphate, Jiao YaPhosphate, bicarbonate, metaborate, biborate, tetraborate, pentaborate, and its derivative or composition.It is describedAmine substitute materials are dissolvable in water in water or the aqueous solution of one or more salt, the organic solution of salt, the aqueous solution of alkali, alkali it is organicIn solution, including but not limited to alkali salt, ammonium salt, alkanolamine, alkaline earth salt, urea, alkali metal phosphate, acid phosphite,Phosphite, phosphorous acid derivative (phosphonite), hypophosphites, phosphonate, superphosphate, pyrophosphite, carbonic acidSalt, bicarbonate, borate, metaborate, biborate, tetraborate, pentaborate or its derivative.The amine substitutesMaterial is also dissolvable in water the organic substance for including one or more components, and the component includes but is not limited to alcohol, ethylene glycol, alkaneHydrocarbon, unsaturated hydrocarbon, ether, ester, aldehyde, ketone, glycol ether, alkylene carbonate, carbonic diester, sulfolane, and its it is derivativeThing, for example, ionic liquid, polymer, organic silicon solvent, organic fluorous solvent.The amine substitute materials be also dissolvable in water it is a kind of orA variety of amine, or other one or more amine substitute materials, such as amino acid, amino-acid salt, acid amides, alkali salt, alkaline earth salt, ammoniumSalt, urea, alkali metal phosphonate, carbonate, borate, acid phosphite, phosphite, phosphorous acid derivative(phosphonite), hypophosphites, phosphonate, superphosphate, pyrophosphite, bicarbonate, metaborate, hypoboric acidSalt, tetraborate, pentaborate.
In one embodiment of the invention, the absorbent includes the aqueous solution of carbonate or/and borate.
In another embodiment of the present invention, the absorbent includes the water-soluble of amine, carbonate or/and borateLiquid, alkali the aqueous solution in.
In another embodiment of the present invention, the absorbent include amine, alcohol, carbonate or/and borate water/In organic solution, water/organic solution of alkali.
In another embodiment of the present invention, the absorbent includes the one or more being dissolved in a kind of solventThe mixture of amine and one or more amine substitutes.The solvent can be any one in for example foregoing solvent.
In the embodiment of the application, the absorbent includes amine aqueous solution, amine substitute or its mixture, instituteCategory solution concentration is selected from the group being made up of following percentage：0.01%th, 0.1%, 1%, 5%, 10%, 15%, 20%, 25%,30%th, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 90% etc..
According to embodiment of the present invention, when the sour gas contacts with absorbent, the sour gas is with physicsMethod and/or chemical method are absorbed.After Physical Absorption, the sour gas is absorbed in absorbent, mainly with without changingModified state is learned to be present in concentration amine phase or concentration amine substitute phase.However, after chemical absorbing, the sour gas is inhaledClose in absorbent, be mainly present in state after being chemically modified in concentration amine phase or concentration amine substitute materials phase, alsoIt is to say, is present in amine or the amine substitute and the reacted reactant of sour gas.
In one embodiment of the invention, amine or the amine substitute and the reacted reaction product base of sour gasDo not dissolved in sheet in the solvent.
In another embodiment of the present invention, amine or the amine substitute and the reacted reaction product of sour gasIt is dissolved in the solvent.
When using amine in the absorbent, the concentration amine mutually includes amine of the concentration higher than initial concentration and absorbedSour gas, the concentration amine can be amine or chemically modified amine, such as by the chemistry between amine and sour gasCaused reaction product after reaction.The concentration amine can mutually exist with a single-phase form, for example, a kind of amine aqueous solution.It is described denseContracting amine mutually can also include multiphase.The absorbed sour gas is accumulated in the concentration amine phase.
Similarly, when using amine substitute in the absorbent, the concentration amine substitute is mutually higher than comprising concentrationThe concentration amine substitute and absorbed sour gas of initial concentration, it is described concentration amine substitute can be the substitute or itsChemical modification, for example, reaction product caused by a kind of chemical reaction as between the substitute and sour gas.The quiltThe sour gas of absorption includes sour gas or its chemical modification, for example, one kind is by between the substitute and sour gasChemical reaction caused by reaction product.The concentration amine substitute can mutually exist with a single-phase form, for example, a kind of denseContracting amine substitute solution.The concentration amine substitute mutually can also include multiphase.The absorbed sour gas accumulates in describedConcentrate in amine substitute phase.
After the absorbent absorbs sour gas, as sour gas is removed or is significantly reduced, purified gasBody mixture is discharged from absorptive unit.The purified admixture of gas being discharged can be received according to the purpose of userCollection or processing.
After absorbent absorbs sour gas, the material in the absorptive unit is transported to upgrading unit.Then divideFrom unit, in separative element, concentration amine phase or concentration amine substitute are mutually separated from the remainder of absorbent.The concentrationAmine phase or concentrate amine substitute phase forming process can before the material in the absorptive unit is transported to upgrading unit,Among or afterwards.
In another embodiment of the present invention, it is mutually formed completely in the concentration amine phase or concentration amine substituteAfterwards, described material is just transported to separative element.
In one embodiment of the invention, before the concentration amine phase or concentration amine substitute are mutually formed completely,Described material is transported to separative element.
In view of existing disclosure, concentration technique known to those skilled in the art of the present technique's use and phase detachment technique can be achievedThe concentration and separation.For example, phase conversion method (Phase Transitional Method), phase transformation can be used in method for concentrationChange method (Phase Change Method), method of evaporating, gasification process, method for crystallising, membrane separating method, pervaporation, extractionTake, filter method, method for concentration also includes passing through temperature change, pressure change, change in concentration, carrying caused by changes in solubilityDense process, and any equipment of concentration can be provided.
For isolation technics, for example, the concentration based on phase, by knock-out drum, you can concentration amine is separated.Also can be based onOther characteristics of phase, such as by using the film different with the remainder permeability of absorbent to concentration amine phase, you can will be denseContracting amine is separated.Further, the Vltrasonic device that the concentration amine can be mutually combined by aid dispersion is separated.
The separating step of the present invention can by using it is one or more it is well known in the art, separated suitable for batch liquid phase thingPhase settler or phase-separating device complete.Some examples include simple settler, filter, whizzer, membrane filtrationDevice, ultrasonic device etc..
After releasing, the remainder of the absorbent mainly includes solvent.The remainder of the absorbent also wrapsAmine or amine substitute containing concentration well below initial concentration.The remainder of the absorbent may also contain on a small quantityAbsorbed sour gas.After releasing, the remainder of the absorbent is recycled to absorptive unit to reuse.
Separated concentration amine phase or concentration amine substitute are mutually sent to regeneration unit, described in the regeneration unitConcentration amine mutually produces or regenerated amine and sour gas through processing.Use for reference embodiment disclosed by the invention, the artTechnical staff can use known renovation process to realize the regeneration technology.Typical renovation process includes but is not limited to heat pointSolution, air- extraction, vaporizing extract process, vacuum method, the way of distillation, handled by membrane contactor (membrane contractor), oozedSaturating gasification, pressure differential method, microwave method, and the combination of above method.It is to be understood that in view of existing disclosure, the art skillArt personnel can also use other renovation process in regeneration technology.
The sour gas of the regeneration is collected or handled according to the purpose of user.The amine or amine of the regenerationSubstitute materials are recyclable to be recycled to absorptive unit to reuse.
On the other hand, the present invention relates to a kind of system for the admixture of gas depickling containing sour gas.The systemSystem includes absorptive unit, upgrading unit, separative element and regeneration unit as described above.
According to embodiment of the present invention, the deacidifying process can be used for removing unpurified acidity from admixture of gasGas, in the deacidifying process, the sour gas can be handled more effectively.On the other hand, the reality according to the present inventionScheme is applied, the deacidifying process can be also used for more effectively collecting sour gas interested from admixture of gas.
In one embodiment of the invention, the solvent in absorbent has the absorption rate for improving the sour gasEffect.The sour gas is inhaled into the ratio of absorbent higher than the speed that it is directly absorbed by amine.
In one aspect of the invention, the reason for energy consumption for regeneration technology is reduced is：Only partially absorb agent(the concentration amine phase) needs to regenerate, and the remainder of the absorbent can rapidly cycle back in absorptive unit and repeat to makeWith.
Fig. 1 illustrates the particular of the present invention, and a kind of gas containing the sour gas to be removed is mixedCompound 1 and a kind of absorbent 3 are positioned in absorptive unit 10.In the absorptive unit 10, the admixture of gas 1 and absorptionAgent 3 contacts with each other.In the absorptive unit 10, after the sour gas is absorbed by absorbent 3, purified gas mixingThing 2 is discharged out the absorptive unit 10.Rich gas absorbent 5 is admitted to upgrading unit 20, and upgrading unit 20 is used to inhale rich gasReceive agent to concentrate to form concentration amine phase, subsequently into separative element 30.Separative element 30 is used to divide from the remainder 4 of absorbentFrom concentration amine phase 6.After releasing, the remainder 4 of the absorbent includes wholly or largely component in solvent, a small amount ofDo not include amine, a small amount of or do not include absorbed sour gas either, with or without further handling, be recycled toAbsorptive unit 10 is with reuse.Separated concentration amine phase 6 comprising it is most or all of, by or without chemical modificationAmine and absorbed sour gas, perhaps also one or more solvents component, for regeneration treatment.
Referring to Fig. 1, the separated concentration amine phase 6 is sent to regeneration unit 40, described in the regeneration unit 40Concentration amine phase 6 is reproduced, and absorbed sour gas 12 is isolated from concentration amine phase, and the concentration amine of remainder is mutually lean gasPhase 14.After the absorbed sour gas 12 is further processed, it can be handled or received according to the purpose of userCollection.The poor gas phase 14 includes the component of the amine, perhaps also one or more solvents of regeneration, with or without further placeReason, it is recycled to absorptive unit 10 to reuse.
According to other embodiments of the present invention, absorptive unit 10 and upgrading unit 20 can turn into a unit,
According to other embodiments of the present invention, upgrading unit 20 and separative element 30 can turn into a unit,
As shown in figure 1, the remainder 4 of the absorbent from separative element 30 and the poor gas phase 14 from regeneration unit 40Mixed in blender 50.Then, the absorbent 3 of generation is cycled back into absorptive unit 10 to reuse.According to the present inventionOther embodiments, the remainder 4 and poor gas phase 14 of the absorbent need not can together be mixed, can circulated respectively firstAbsorptive unit 10 is back to reuse.
Although not showing in Fig. 1, in view of existing disclosure, in addition to the component through circulation and stress of the absorbent 3, abilityField technique personnel can add the component of extra one or more absorbents 3, be damaged with compensation during deacidifying processOne or more components of mistake.
According to embodiment of the present invention, the exhaust passage (stack) in existing power plant or other kinds of equipment can quiltsTransform or change into absorptive unit.According to embodiment of the present invention, the exhaust passage (stack) can also be transformed into or turnChemical conversion includes the single tower of absorptive unit, separative element and regeneration unit.
Following examples are used to illustrate the present invention, but are in no way intended to limit the use range of the present invention.
Embodiment 1
The absorbent by volume ratio 20% amine (monoethanolamine is Monoethanolamine (MEA)) and volume ratio80% water composition.At 25~45 DEG C, under the conditions of 1atm, in packed absorber, by absorbent and include sour gas (twoCarbonoxide) admixture of gas contact.Absorbent absorbs sour gas and forms rich gas (carbon dioxide) absorbent, uses UF membraneMethod, the rich gas absorbent flowed out out of packed tower is concentrated to form concentration amine phase in the concentration amine phase, whole MEA (bagsInclude not chemically modified MEA and MEA and CO2Reaction product) concentration be about volume ratio 80%, water 20%.WillConcentration amine mutually separates from the remainder of absorbent.After separation, the remainder of the absorbent include most of water,Also small part MEA and absorbed CO2,
By the separated concentration amine phase transfer to regenerator, and by heating the method for the concentration amine phase to describedConcentration amine is mutually handled to obtain the MEA and CO of regeneration2.The MEA of regeneration is mixed with the remainder of absorbent.By described inMixture is cycled back in packed absorber to complete circulation.
Embodiment 2
The present embodiment displaying absorbs CO by carbonate aqueous solution2。
A kind of absorbent being made up of carbonate aqueous solution.At 50 DEG C, under the conditions of 1atm, in packed absorber, by instituteState absorbent and contacted with including the admixture of gas of sour gas (carbon dioxide).Absorbent absorbs sour gas and forms rich gas(carbon dioxide) absorbent, using membrane separating method, the rich gas absorbent flowed out out of packed tower is concentrated to form concentration carbonic acidSalt phase is in the concentration carbonate facics, whole carbonate (including not chemically modified carbonate and carbonate and CO2Reaction product, bicarbonate).Concentration carbonate facics is separated from the remainder of absorbent.After separation, the absorptionThe remainder of agent includes most of water, also has small part carbonate and bicarbonate.
The separated concentration carbonate facics is transferred to regenerator, and by heating the side of the concentration carbonate facicsMethod is handled to obtain the carbonate and CO of regeneration the concentration carbonate facics2.By the carbonate of regeneration and absorbentRemainder mixes.The mixture is cycled back in packed absorber to complete circulation.
Embodiment 3
The absorbent by volume ratio 30% amine (monoethanolamine is MEA+ piperazines (a small amount of)) and volume ratio 70% is moltenAgent (isooctanol) forms.At 25~45 DEG C, under the conditions of 1atm, in stirring absorptive unit (stirring cell absorptionUnit in), absorbent is contacted with including the admixture of gas of sour gas (carbon dioxide).Monoethanolamine in absorbent(MEA) spontaneous to be condensed into concentration amine phase, the concentration amine mutually includes MEA and MEA and CO2Reaction product.
After absorption, by absorbent described in gravitational settling, concentration amine is mutually separated from the remainder of absorbent.After separation, the remainder of the absorbent includes most of isooctanol, perhaps also has part MEA and absorbed CO2,Receipts are recycled to absorptive unit to reuse.In the concentration amine phase, whole MEA (including not chemically modified MEAAnd MEA and CO2Reaction product) concentration be about volume ratio 60-70%.
By the separated concentration amine phase transfer to regenerator, and by heating the method for the concentration amine phase to describedConcentration amine is mutually handled to obtain the MEA and CO of regeneration2.The MEA of regeneration is mixed with the remainder of absorbent.By described inMixture circulation and stress extremely stirs absorptive unit to complete to circulate.
Collect the CO of regeneration technology flow release2。
Embodiment 4
The absorbent by volume ratio 30% amine (include the piperazine of 98% monoethanolamine 1%, 0.1% potassium carbonate,0.9% water) and volume ratio 70% solvent (isooctanol) composition.At 25~45 DEG C, under the conditions of 1atm, in stirring absorptive unitIn (stirring cell absorption unit), absorbent is mixed with including the gas of sour gas (carbon dioxide)Compound contacts.Spontaneous be condensed into of monoethanolamine (MEA) in absorbent concentrates amine phase, and the main component of the concentration amine phase includesMEA, MEA and CO2Reaction product, and other compositions.
After absorption, by absorbent described in gravitational settling, concentration amine is mutually separated from the remainder of absorbent.After separation, the remainder of the absorbent includes most of isooctanol, perhaps also has part MEA and absorbed CO2,Receipts are recycled to absorptive unit to reuse.In the concentration amine phase, composition is mainly MEA, piperazine and potassium carbonate (bagInclude not chemically modified MEA, piperazine and potassium carbonate and MEA, piperazine, potassium carbonate, and CO2Reaction product).
By the separated concentration amine phase transfer to regenerator, and by heating the method for the concentration amine phase to describedConcentration amine is mutually handled to obtain the MEA of regeneration, piperazine, potassium carbonate and CO2.By the MEA of regeneration and the remainder of absorbentDivide mixing.The mixture circulation and stress is extremely stirred to absorptive unit to complete to circulate.
Collect the CO of regeneration technology flow release2。
It is to be appreciated that in the case of without departing from theory scope of the present invention, those skilled in the art can be to the aboveThe embodiment of description makes change.Thus, it is to be understood that the present invention is not limited to disclosed particular, andIt is intended to cover in the variants and modifications defined in appended claim within the spirit and scope of the invention.