CN103182241B - A kind of high-viscosity alcohol amine aqueous solution absorbs CO 2process - Google Patents
A kind of high-viscosity alcohol amine aqueous solution absorbs CO 2process Download PDFInfo
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- CN103182241B CN103182241B CN201210232722.0A CN201210232722A CN103182241B CN 103182241 B CN103182241 B CN 103182241B CN 201210232722 A CN201210232722 A CN 201210232722A CN 103182241 B CN103182241 B CN 103182241B
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- viscosity
- absorbent
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- absorbing liquid
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The present invention relates to a kind of high-viscosity alcohol amine aqueous solution and absorb CO
2process, concrete steps are, by CO
2be that 0.1 ~ 3m/s is by straight channel vertical plate regular packed tower with the mist of air with gas speed, with high viscosity (μ>=3mPa.s) the absorbing liquid adverse current declined or and flow and contact, complete absorption, the adoptable liquid spraying density of this technique is 10 ~ 100m
3/ (m
2h), spendable absorption temperature is 0 ~ 70 DEG C, CO
2the volume fraction accounting for mist is 5% ~ 100%.The lower sticky absorbent of the mass tranfer coefficient of absorbent is the invention enables at least to improve 30% ~ 50%, absorption efficiency improves more than 50%, corresponding absorbing liquid thermal capacitance at least reduces by 15%, desorb energy consumption decline 10% ~ 20%, thus energy consumption needed for whole technique comparatively conventional suction technique significantly reduce.
Description
[technical field]
The present invention relates to chemical process technical field, specifically, is that a kind of high-viscosity alcohol amine aqueous solution absorbs CO
2process.
[background technology]
In recent years, CO
2reduction of discharging problem is more and more subject to the extensive concern of international and domestic society, how effectively to reduce CO
2discharge is human society common difficulty urgently to be resolved hurrily.In numerous discharge-reducing methods, the chemical absorption method being absorbent with alcamines solution be generally acknowledge at present be easy to one of reduction of discharging means realizing heavy industrialization most.But existing absorption techniques ubiquity energy consumption high, running cost remains high this actuality difficult problem.Report is had to think, for a power plant, even if adopt present stage state-of-the-art CO
2trapping technique, required energy consumption will make its generated energy lose 30%, and unit price of power goes up 80%.Therefore, new CO is explored
2absorption technique is significant.
In existing absorption-desorb integral process, desorption temperature is usually at about 120 DEG C, and desorb energy consumption accounts for more than 80% of total energy consumption usually.Trace it to its cause, in general alcamines absorbent, the content of water is usually more than 50%, have even up to 80%, because specific heat of water holds comparatively large, cause desorption process to need to consume a large amount of energy.Alkanolamine solution absorbs CO
2a chemical reaction process in essence.Generally speaking, an important channel of absorbent strengthening improves its concentration exactly, can make reaction rate accelerates so on the one hand, the absorptive capacity of unit volume absorbent can be made to strengthen on the other hand, and consumption reduces, and table 1 is CO
2solubility and absorption rate are with the variation relation of N methyldiethanol amine (MDEA) concentration and viscosity.In addition, thermal capacitance due to organic solution is generally only 50% of water, if content of organics in raising absorbing liquid, its thermal capacitance will obviously decline, for MEA (MEA) and diethanol amine (DEA) aqueous solution, 38 DEG C time, when hydramine mass fraction brings up to 50% by 15%, solution specific heat capacity can decline 15%, and the energy consumption thus in its follow-up desorption process also will significantly decline.But, for CO
2absorption reaction, has again the particularity of himself, the absorbent used at present, general viscosity is comparatively large, and table 2 is several conventional alcamines absorbent viscosity numbers at normal temperatures, and as shown in Table 1, when the concentration of absorbent increases, the corresponding increase of its viscosity will inevitably be made.
But it is generally acknowledged low sticky be basic demand to absorbent, be carrying out smoothly of ensureing to absorb, current CO
2the absorbent that absorption technique uses is commonly low sticky absorbent, and Chinese Patent Application No. 200910235421.1 is disclosed, and " a kind of three-phase circulating fluidized bed ammonia process catches the CO in flue gas
2method and device " absorbent that adopts is the ammoniacal liquor of 10% ~ 30%, reaction unit is three-phase circulating fluidized bed.The CO that Chinese Patent Application No. 200920159721.1 disclosed " purifying crude synthetic gas with low-temperature methanol system " adopts
2absorbent is methyl alcohol.In addition, for the modification of alcamines absorbent, the method of adding activating agent or modifying agent is generally adopted to improve the absorbent properties of original solvent at present, for " a kind of renewable/non-renewable acid gas absorbent " disclosed in U.S. Patent number US2011/0168496, by alkanolamine solution and solubility syrup concentrate (Soluble Molasses Condensate, SMC) by a certain percentage interworking become renewable or non-renewable absorbent to improve absorbent properties.For the preparation of Regeneratable absorbent, on the basis of original alkanolamine solution, only add the SMC of about 5%, make the water content in solution still higher, its follow-up energy of desorption consumption cannot effectively decline.In order to improve CO
2absorption technique is to the adaptability of absorbing liquid viscosity, and the present invention absorbs CO with diethanol amine (DEA)
2for example, propose the absorption technique that a kind of raising absorbing liquid newly sticky (dense) is spent, and improve its mass-transfer efficiency, and then realize the energy-saving and cost-reducing of whole desorb-absorption integrated technique.
Table 1 CO
2solubility and the relation between absorption rate and MDEA solubility
Viscosity under several conventional alcamines absorbent normal temperature of table 2
[summary of the invention]
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of high-viscosity alcohol amine aqueous solution to absorb CO
2process.
The object of the invention is to be achieved through the following technical solutions:
Principle of the present invention is: while absorbing liquid viscosity increases, concentration also increases thereupon.For chemical absorbing, the increase of reactant concentration is conducive to improving chemical absorbing speed, namely improves enhancement factorβ, on the other hand along with the increase k of viscosity
lcorrespondingly reduce, due to liquid phase mass transfer coefficient K
l=β k
l.In certain solution viscosity range, along with the increase of hydramine concentration, the amplitude that enhancement factorβ increases is greater than k
lthe range of decrease, now macroscopically showing as mass tranfer coefficient K
lincrease with solution viscosity is amid a sharp increase on the contrary.Because content of organics obviously increases, corresponding desorb energy consumption greatly reduces.
A kind of high-viscosity alcohol amine aqueous solution absorbs CO
2process, concrete steps are, by CO
2be that 0.1 ~ 3m/s is by straight channel vertical plate regular packed tower (hereinafter referred to as packed tower) with the mist of air with gas speed, high sticky absorbing liquid (μ>=3mPa.s) adds from packed tower top from tubular type or groove type distributor with certain flow, be membrane type uniform flow along filler, the back flow of gas of the high viscosity absorbing liquid and the rising that decline or and flow and contact, gas is that cross-flow moves upward along filler passage, complete absorption, the adoptable liquid spraying density of this technique is 10 ~ 100m
3/ (m
2h), spendable absorption temperature is 0 ~ 70 DEG C, CO
2the volume fraction accounting for mist is 5% ~ 100%.For ensure high viscosity absorbing liquid in falling film without emulsification, to foam or foamed phenomenon occurs and increases without additional energy, the equipment that the present invention adopts is the straight channel vertical plate regular packed tower having wall and alternately coexist without wall liquid film.
Described absorbing liquid is the solution of alcamines absorbent, and viscosity is greater than 3mPa.s;
Described alcamines absorbent is monoethanolamine, diethanol amine, triethanolamine, one or more in diisopropanolamine (DIPA) or methyl diethanolamine.
Compared with prior art, good effect of the present invention is:
The lower sticky absorbent of the mass tranfer coefficient of absorbent is the invention enables at least to improve 30% ~ 50%, absorption efficiency improves more than 50%, corresponding absorbing liquid thermal capacitance at least reduces by 15%, desorb energy consumption decline 10% ~ 20%, thus energy consumption needed for whole technique comparatively conventional suction technique greatly reduce.
[accompanying drawing explanation]
Fig. 1 is high according to an exemplary embodiment of the present sticky (dense) degree absorbing liquid CO
2absorption technique schematic diagram;
Liquid phase mass transfer coefficient K under the different sprinkle density of Fig. 2
lwith the variation diagram of DEA solution viscosity, 2a is 30m
3/ (m
2h); 2b is 60m
3/ (m
2h); 2c is 100m
3/ (m
2h);
Label in accompanying drawing is respectively: 1, CO
2steel cylinder, 2, air, 3, gas flowmeter, 4, Water Tank with Temp.-controlled, 5, gas mixer chamber, 6, packed tower, 7, fluid flowmeter, 8, head tank, 9, drier, 10, CO
2infrared spectrum analyser, 11, centrifugal pump, 12, fluid reservoir.
[detailed description of the invention]
A kind of high-viscosity alcohol amine aqueous solution of the present invention is below provided to absorb CO
2the detailed description of the invention of process.
Embodiment 1
Refer to Fig. 1,2a, 2b, 2c, a kind of high-viscosity alcohol amine aqueous solution absorbs CO
2process, concrete steps are, by CO
2mist with gas speed be 0.1 ~ 3m/s by packed tower 6, with the high viscosity absorbing liquid adverse current declined or and flow and contact, complete absorption.
This example use GAS ABSORPTION technique as shown in Figure 1, CO
2steel cylinder 1 and air 2 by gas flowmeter 3 inside Water Tank with Temp.-controlled 4 after water vapour is saturated, abundant mixing is reached in gas and vapor permeation indoor 5, entered by the bottom of packed tower 6 again, flow out with the top from regular packed tower 6 after diethanol amine (DEA) reactant aqueous solution, effluent air drying enters CO
2infrared spectrum analyser 10.Absorbing liquid first delivers to head tank 8 by fluid reservoir 12 through centrifugal pump 11, then enters packed tower 6 through head tank 8, and gas-liquid two-phase gross contact area is 2*100*600mm.
CO in this example
2volume fraction is 15 ~ 45%, and diethanolamine solution viscosity is 1 ~ 15mPa.s, and corresponding mass mark is 5 ~ 56% gas flow rates is 0.2 ~ 1m/s, and absorbing liquid sprinkle density is 30 ~ 100m
3/ (m
2.h), experimental temperature is 30 ± 0.5 DEG C.Result as shown in Figure 2, is 2a, 2b, 2c.
From result, at different CO
2under volume fraction and liquid spraying density, liquid phase mass transfer coefficient K
lchange with DEA solution viscosity presents identical rule, in the range of viscosities of 1-10mPa.s, along with the increase of solution viscosity, and liquid phase mass transfer coefficient K
lalso increase thereupon, when absorbing liquid viscosity is greater than 10mPa.s, liquid phase mass transfer coefficient K
lslightly declined, but still apparently higher than the K of (1 ~ 2mPa.s) under low viscosity
lvalue.Take viscosity as the K that 1.8mPa.s DEA solution is corresponding
lvalue for benchmark, at identical liquid spraying density (30,60 and 100m
3/ (m
2.h)), viscosity is the K that 10mPa.s DEA solution is corresponding
lvalue be respectively its 1.6,1.5,1.5 times, viscosity is the K that 15mPa.s DEA solution is corresponding
lvalue be respectively its 1.5,1.4,1.3 times, show that height that the present invention proposes glues absorption technique and effectively can promote mass transfer.
In addition, it is worth mentioning that, under experimental temperature, when the viscosity of diethanol amine (DEA) solution brings up to 15mPa.s by 1mPa.s, the specific heat capacity of solution declines about 17%, follow-up desorb energy consumption declines 15%, and comparatively traditional handicraft is significantly energy-saving and cost-reducing to show height that the present invention proposes to glue absorption technique.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise; can also make some improvements and modifications, these improvements and modifications also should be considered within the scope of protection of the present invention.
Claims (1)
1. a high-viscosity alcohol amine aqueous solution absorbs CO
2method, is characterized in that, concrete steps are, by CO
2with the mist of air with gas speed be 0.1 ~ 3m/s by straight channel vertical plate regular packed tower, with the high viscosity absorbing liquid adverse current declined or and flow and contact, complete absorption; The liquid spraying density adopted is 10 ~ 100m
3/ (m
2h), the absorption temperature of use is 0 ~ 70 DEG C, CO
2the volume fraction accounting for mist is 5% ~ 100%;
Described absorbing liquid is the solution of hydramine absorbent, and viscosity is greater than 3mPa.s;
Described hydramine absorbent is monoethanolamine, diethanol amine, triethanolamine, one or more in diisopropanolamine (DIPA) or methyl diethanolamine.
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MDEA混合胺法脱碳在珠海天然气液化项目中的应用;曾树兵等;《石油与天然气化工》;20071231;第36卷(第6期);第485-487页 * |
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