CN104437050A - Application of heat-stability carbonic anhydrase to circular absorption-desorption of CO2 by catalyzing organic amine solution - Google Patents
Application of heat-stability carbonic anhydrase to circular absorption-desorption of CO2 by catalyzing organic amine solution Download PDFInfo
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- CN104437050A CN104437050A CN201410641839.3A CN201410641839A CN104437050A CN 104437050 A CN104437050 A CN 104437050A CN 201410641839 A CN201410641839 A CN 201410641839A CN 104437050 A CN104437050 A CN 104437050A
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Abstract
The invention provides application of heat-stability carbonic anhydrase to circular absorption-desorption of CO2 by catalyzing an organic amine solution, and belongs to the field of CO2 emission reduction treatment. The heat-stability carbonic anhydrase has an amino acid sequence of SEQ ID NO:2 shown in specification. The CO2 can be circularly absorbed and desorbed by organic amine by using carbonic anhydrase (PaCA) obtained by genetic recombination expression; carbonic anhydrase has the relatively stable catalyzing capability in the process of circularly absorbing and desorbing the CO2 by the organic amine; and the relatively good stability still can be kept after the carbonic anhydrase is circulated for multiple times in the application, so that the energy investment can be well saved.
Description
Technical field
The invention belongs to CO
2reduce discharging process field, relate to a kind of heat endurance carbonic anhydrase particularly at catalysis By Amine Solutions cyclic absorption-desorb CO
2in application.
Background technology
CO
2cause the topmost greenhouse gases of global warming.Over nearly more than 100 years, the heavy industrialization process of the mankind causes greenhouse gases to enter air without limit, along with the minimizing of the forest reserves, and CO
2the rising of content has exceeded the absorbability of plant and ocean.Probably there is the CO of 24,000,000,000 tons in the annual whole world
2discharge, and the discharge capacity of nearly 40% all comes from the power plant of countries in the world.According to statistics, China has more than 3,000 coal power plant (about more than 5,000, the whole world) at present, for the power plant of 300 mw scale, its generating efficiency is generally about 35%, generating 105 megawatt per hour, and discharge nearly 290 tons of carbon dioxide (1 ton of coal combustion produces 3.67 tons of carbon dioxide in theory, actual generation about 2.34 tons of carbon dioxide).More than 300 hundred million tons of carbon dioxide are discharged every year altogether in the whole world, cause serious greenhouse effects.Therefore, the seizure trans-utilization of carbon dioxide is very urgent.
Adopt the CO in effective means recovery waste gas
2effectively can improve greenhouse effects.How to reduce and catch CO
2cost and turned waste into wealth, realize its separation and recovery and comprehensive utilization, one of 21 century of paramount importance energy and environment problem will be become.
For the flue gas CO of industrial discharge
2, generally have three kinds of method for catching, namely catch before burning; Catch after oxygen-enriched combusting and burning, cannot realize commercialization due to first two method for catching high cost, after the burning that development is comparatively ripe, trapping generally adopts absorption process to carry out decarburization.Amine process becomes the current CO be uniquely commercially used due to advantages such as uptake are large, equipment investment is less, price is comparatively cheap, reducible
2trapping technique.Still there is the problems such as desorb energy consumption is high, equipment is huge in this trapping technique current, seriously governs the large-scale promotion of smoke carbon dioxide capture technology.For solving the too high problem of tradition trapping process cost, carbonic anhydrase (CA) has been applied in this technology as biocatalyst.CA is known catalysis CO
2hydration generates HCO
3 -the fastest enzyme of speed, its catalytic rate constant can reach 10
6s
-1.Existing many research both at home and abroad proves that CA effectively can promote that organic solvent absorbs CO
2efficiency, but the application sucted in solution for CA is still few.The research of Blais and Rogers etc. shows, if add CA in water-soluble solvent (as tertiary amine etc.), the desorption process of solvent just can carry out at a lower temperature, namely greatly reduces CCU (CO
2capture and Utilization, CCU) required for energy.Current trapping technique is then mainly based upon solvent in two independently unit: CO
2absorption tower and CO
2carry out between Analytic Tower the basis of circulating absorbs CO
2cA catalytic absorption and desorption process is simultaneously added in cyclic process, can reduce reaction temperature thus reduce energy consumption, but this is higher to the stability requirement of enzyme, comprise to high concentration By Amine Solutions and in low temperature absorption and desorption under high temperature cyclic process the tolerance of the environment such as temperature.There is Canadian CO abroad
2solution Inc has delivered a series of patent, and the patent CA2803959 delivered for 2012 improves temperature stability and organic solvent tolerance by chemical modification carbonic anhydrase, thus improves MDEA absorption CO
2efficiency.
Summary of the invention
In order to solve the problem, the object of this invention is to provide a kind of heat endurance carbonic anhydrase at catalysis By Amine Solutions cyclic absorption-desorb CO
2in application.
A kind of carbonic anhydrase (PaCA) catalysis organic amine cyclic absorption and desorb CO in this application method of the recombinant expressed acquisition of applying gene of the present invention
2, apply this enzyme at organic amine cyclic absorption and desorb CO
2in process, there is more stable catalytic capability; In application of the present invention, this enzyme still can keep good stability after repeatedly circulating, and saves Energy input.
Technical scheme of the present invention is as follows:
A kind of heat endurance carbonic anhydrase is at catalysis By Amine Solutions cyclic absorption-desorb CO
2in application, described heat endurance carbonic anhydrase is the amino acid sequence shown in SEQ ID NO:2.
According to heat endurance carbonic anhydrase of the present invention at catalysis By Amine Solutions cyclic absorption-desorb CO
2in application, the method for this application is comprise the steps:
(1) in the reactor that By Amine Solutions is housed, add the enzyme liquid of described carbonic anhydrase, addition is 15-75mL/L By Amine Solutions, and the weight weighing mixed solution in reactor is M0, at 25-40 DEG C of (CO
2trapping be low temperature absorption, desorption under high temperature, under apparatus of the present invention condition, normal temperature has better assimilation effect) under in the mixed solution of described reactor, pass into CO
2, stir, detect pH, during no longer change stable to pH value, By Amine Solutions being weighed as to M1 and measuring volume is V1;
(2) absorption terminates rear rising temperature of reactor and starts desorb CO to 50-100 DEG C
2, stir, detect pH change, during pH value rising about 1.0, desorption process terminates, and measuring volume to By Amine Solutions is V2;
(3) if V1 is greater than V2, then add water to V1 volume to the By Amine Solutions in step (2), then, to the By Amine Solutions after step (2) desorb maybe this By Amine Solutions having added water be weighed as M2;
(4) in described cyclic absorption-desorb, the amount of the carbon dioxide of absorption is M1-M0, and after absorbing, Desorption of Carbon Dioxide amount is M1-M2;
(5) By Amine Solutions after step (3) desorb is down to room temperature, is recycled to the absorbing liquid that reactor absorbed as next time, repeat step (1)-(5), so circulate.
According to heat endurance carbonic anhydrase of the present invention at catalysis By Amine Solutions cyclic absorption-desorb CO
2in application, the method for preferably this application is comprise the steps:
(1) in the reactor that By Amine Solutions is housed, add the enzyme liquid of described carbonic anhydrase, addition is 15-75mL/L By Amine Solutions, at 25-40 DEG C, pass into CO in the mixed solution of described reactor
2, stir, detect pH, no longer change to pH value is stable;
(2) absorption terminates rear rising temperature of reactor and starts desorb CO to 50-100 DEG C
2, stir, detect pH change, pH value raises about 1.0 desorbs (noting unified in full, is not resolve) process and terminates;
(3) By Amine Solutions after step (2) desorb is down to room temperature, is recycled to the absorbing liquid that reactor absorbed as next time, repeat step (1)-(3), so circulate.
According to described heat endurance carbonic anhydrase at catalysis By Amine Solutions cyclic absorption-desorb CO
2in application, described desorption temperature is preferably 60-80 DEG C.In desorption process, the too low CO that desorb can occur of temperature
2be gradually resorbed effect, and the too high energy consumption that causes of temperature is high, fund input is large.
According to described heat endurance carbonic anhydrase at catalysis By Amine Solutions cyclic absorption-desorb CO
2in application, described carbonic anhydrase adds when first time absorbs, and the enzyme of described enzyme liquid concentration of living is 32000U/mL.
According to described heat endurance carbonic anhydrase at catalysis By Amine Solutions cyclic absorption-desorb CO
2in application, described By Amine Solutions is selected from the one in monoethanolamine (MEA), diethanol amine (DEA), methyl diethanolamine (MDEA), triethanolamine (TEA), piperazine (PZ).
Described By Amine Solutions concentration is: 1-6mol/L, and the too low uptake of concentration is few, and excessive concentration mass transfer causes absorption efficiency low slowly.
According to described heat endurance carbonic anhydrase at catalysis By Amine Solutions cyclic absorption-desorb CO
2in application, preferably, described By Amine Solutions is selected from the one in monoethanolamine (MEA), methyl diethanolamine (MDEA), piperazine (PZ).
According to described heat endurance carbonic anhydrase at catalysis By Amine Solutions cyclic absorption-desorb CO
2in application, in described step (1) every 5-20min detect pH.
According to described heat endurance carbonic anhydrase at catalysis By Amine Solutions cyclic absorption-desorb CO
2in application, in described step (2) every 1-15min detect pH.
According to described heat endurance carbonic anhydrase at catalysis By Amine Solutions cyclic absorption-desorb CO
2in application, the detection of pH is measured at 27-28 DEG C in the described step (2).
According to described heat endurance carbonic anhydrase at catalysis By Amine Solutions cyclic absorption-desorb CO
2in application, the stir speed (S.S.) of described stirring is 200-450rpm.
According to described heat endurance carbonic anhydrase at catalysis By Amine Solutions cyclic absorption-desorb CO
2in application, the desorption time in described step (2) is 20-80min.
According to described heat endurance carbonic anhydrase at catalysis By Amine Solutions cyclic absorption-desorb CO
2in application, described heat endurance carbonic anhydrase is at catalysis By Amine Solutions cyclic absorption-desorb CO
23-8 time capable of circulation.
According to described heat endurance carbonic anhydrase at catalysis By Amine Solutions cyclic absorption-desorb CO
2in application, preferably, described heat endurance carbonic anhydrase is at catalysis By Amine Solutions cyclic absorption-desorb CO
23-5 time capable of circulation.
The present invention also provides a kind of nucleotide sequence as shown in SEQ ID NO:1 of heat endurance carbonic anhydrase described in claim 1 of encoding.
As the restructuring carbonic anhydrase of heterogenous expression in Escherichia coli, this enzyme has reasonable heat endurance and MDEA tolerance, can be used for the cyclic absorption and the desorb that promote carbon dioxide.
Restructuring carbonic anhydrase of the present invention can be applied to other By Amine Solutions desorb CO
2system in, also can be applicable to the cyclic absorption-desorption system under different temperatures.
The present invention simulates industry trapping CO
2in there is the device of certain ratio of height to diameter, directly adopt By Amine Solutions to CO
2first absorb and to heat up desorb to finite concentration again, desorption temperature is adding on the enzymatic basis of carbonic anhydride suitably lower than industrial condition.
Advantageous Effects:
The invention provides a kind of heat endurance carbonic anhydrase at catalysis By Amine Solutions cyclic absorption-desorb CO
2in application, in this application, this restructuring carbonic anhydrase is had at 25 ~ 40 DEG C, promotes carbon dioxide absorption, at 50-100 DEG C, promote carbon dioxide desorption; Enzymatic efficiency is high, carbon dioxide capture speed and the release of carbonate dioxide realized at a lower temperature and regeneration can be accelerated, thus reduce equipment investment (reducing the height of carbon dioxide absorption tower) and reduce energy consumption (resolution temperature of prior art is general all more than 110 DEG C), can be used for carbon capture Plugging Technology Applied, reduce environmental pollution.
The good stability of the restructuring carbonic anhydrase of the present invention's structure, can recycle the absorption and desorption carrying out carbon dioxide in application provided by the invention, still can keep good stability, save Energy input better after repeatedly circulating.
Accompanying drawing explanation
Fig. 1 is in embodiment 2 in PaCA cyclic absorption and desorption process, and 3 cyclic absorption reactions and desorb are reacted pH and compared.
Fig. 2 is in embodiment 3 in PaCA cyclic absorption and desorption process, and 3 cyclic absorption reactions and desorb are reacted pH and compared.
Fig. 3 is in embodiment 4 in PaCA cyclic absorption and desorption process, and 3 cyclic absorption reactions and desorb are reacted pH and compared.
Note: 1-1: once absorb; 1-2: desorb; 2-1: double absorption; 2-2: secondary desorb; Absorb for 3-1: three times; 3-2: three desorbs.
Detailed description of the invention
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.
The preparation of embodiment 1 PaCA enzyme liquid
1.1 culture mediums:
LB solid medium (g/L): yeast extract 5, peptone 10, sodium chloride 10, agar 15
LB fluid nutrient medium (g/L): yeast extract 5, peptone 10, sodium chloride 10
1.2 preparation process
Carbonic anhydrase nucleotide sequence (Seq No.1 is obtained according to Blast comparison, called after PaCA), full genome synthesis is carried out by Nanjing Genscript Biotechnology Co., Ltd. after optimizing, then be connected with plasmid pET21a (Novagen), recombinant plasmid PaCA-pET21a is transformed into BL21 (DE3) competent cell (being purchased from TIANGEN Biotech (Beijing) Co., Ltd.), and picking positive colony list bacterium colony carries out expression and is verified as soluble activating expression.
The Escherichia coli of getting in glycerine pipe line on the flat board with ammonia benzyl resistance LB solid medium.Cultivate 12-16h for 37 DEG C, picking list bacterium colony is transferred in the test tube be equipped with in 5mL LB fluid nutrient medium and cultivates, 37 DEG C, and 200rpm cultivates, OD
600be transferred to when reaching 0.4-0.8 to be equipped with in 400mL LB fluid nutrient medium to expand and cultivate, cultivate bacterium liquid OD
600reach 0.4-0.6, then add the IPTG of final concentration 0.1mM, temperature is adjusted to 30 DEG C of low temperature induction 12h.
Collected by centrifugation thalline (8000rpm, 10min), with the resuspended cleaning twice of PB buffer solution (0.05M, pH7.0), finally uses the resuspended (volume: thalline weight in wet base of certain volume PB buffer solution; 3:1).Ultrasonication 10min (200W, work3s, interval5s).The centrifugal 20min of 12000rpm gets supernatant and namely obtains crude enzyme liquid.Described enzyme liquid is applied in the present invention and following examples.The enzyme concentration alive of described enzyme liquid is 32000U/mL.
Embodiment 2: heat endurance carbonic anhydrase is at catalysis By Amine Solutions cyclic absorption-desorb CO
2in application: material and instrument: reactor is 5L jacketed glass reactor (ratio of height to diameter is 8:1), and Shanghai Ke Xing glass apparatus factory provides.
N methyldiethanol amine (MDEA), analyzes pure; Carbonic anhydrase, company's self-control (PaCA); CO
2gas, Shanghai Xi Qin gas Co., Ltd provides.
The present embodiment adopts cyclic absorption, the method for desorb assesses PaCA catalysis By Amine Solutions absorption and desorption CO
2efficiency and the stability of enzyme.
Experimental program is that normal temperature absorbs-80 DEG C of desorbs (adding 800U/mL PaCA enzyme liquid).Absorption system is 2L3M MDEA solution, passes into CO with the speed of 6L/min to system
2, detect pH every 10min, when pH value surely no longer changes, absorption system weighed.Absorption terminates rear rising temperature of reactor to 80 DEG C and starts desorb CO
2, detect pH change (pH all measures at 27-28 DEG C) every 5min.Reaction system is weighed and is measured volume before desorb, again measures volume after desorb, and the part of minimizing is thought caused by moisture evaporates, and takes quality after desorb after adding water to original volume.After first time, absorption-desorption experiment terminated, lean solution after the desorb of being down to room temperature is recycled to the absorbing liquid that reactor absorbs as second time.Repeat absorption-desorb by above-mentioned steps, carry out 3 circulations altogether.Compare the data analysis collected in each absorption and desorption process, from 3 circulations, absorption reaction and desorb are reacted in pH (Fig. 1) and mass change (table 1) and can be judged that this enzyme has good stability.
Table 1
Embodiment 3: heat endurance carbonic anhydrase is at catalysis By Amine Solutions cyclic absorption-desorb CO
2in application:
Material: MEA (MEA), analyzes pure.Other experiment conditions are identical with embodiment 2.
Experimental program is 30 DEG C and absorbs-60 DEG C of desorbs, and add 900U/mL PaCA enzyme liquid, absorption system is 2L3M MEA solution, passes into CO with the speed of 6L/min to system
2, detect pH every 10min, when pH value surely no longer changes, absorption system weighed.Absorption terminates rear rising temperature of reactor to 80 DEG C and starts desorb CO
2, stir speed (S.S.) is 300rpm, and detect pH change (pH all measures at 27-28 DEG C) every 5min, desorption time is 60min.Reaction system is weighed and is measured volume before desorb, again measures volume after desorb, and the part of minimizing is thought caused by moisture evaporates, and takes quality after desorb after adding water to original volume.After first time, absorption-desorption experiment terminated, lean solution after the desorb of being down to room temperature is recycled to the absorbing liquid that reactor absorbs as second time.
Repeat absorption-desorb by above-mentioned steps, carry out 3 circulations altogether.Compare the data analysis collected in each absorption and desorption process, from 3 circulations, absorption reaction and desorb are reacted in pH (Fig. 2) and mass change (table 2) and can be judged that this enzyme has good stability.
Table 2
Embodiment 4: heat endurance carbonic anhydrase is at catalysis By Amine Solutions cyclic absorption-desorb CO
2in application:
Material: piperazine (PZ), analyzes pure.Other experiment conditions are identical with embodiment 2.
Experimental program is 35 DEG C and absorbs-75 DEG C of desorbs, adds 1000U/mL PaCA enzyme liquid.Absorption system is 2L3M PZ solution, passes into CO with the speed of 6L/min to system
2, detect pH every 10min, when pH value surely no longer changes, absorption system weighed.Absorption terminates rear rising temperature of reactor to 75 DEG C and starts desorb CO
2, stir speed (S.S.) is 380rpm, and detect pH change (pH all measures at 27-28 DEG C) every 5min, desorption time is 60min.
Repeat absorption-desorb by above-mentioned steps, carry out 3 circulations altogether.Compare the data analysis collected in each absorption and desorption process, from 3 circulations, absorption reaction and desorb are reacted in pH (Fig. 3) and mass change (table 3) and can be judged that this enzyme has good stability.
Table 3
The invention provides a kind of heat endurance carbonic anhydrase at catalysis By Amine Solutions cyclic absorption-desorb CO
2in application, in this application, this restructuring carbonic anhydrase is had and promotes carbon dioxide absorption at low temperatures, under high temperature, promote carbon dioxide desorption; Enzymatic efficiency is high, carbon dioxide capture speed and the release of carbonate dioxide realized at a lower temperature and regeneration can be accelerated, thus reduce equipment investment (reducing the height of carbon dioxide absorption tower) and reduce energy consumption (resolution temperature of prior art is general all more than 110 DEG C), can be used for carbon capture Plugging Technology Applied, reduce environmental pollution.The good stability of the restructuring carbonic anhydrase of the present invention's structure, can recycle the absorption and desorption carrying out carbon dioxide in application provided by the invention, still can keep good stability, save Energy input better after repeatedly circulating.
Claims (10)
1. heat endurance carbonic anhydrase is at catalysis By Amine Solutions cyclic absorption-desorb CO
2in application, described heat endurance carbonic anhydrase is the amino acid sequence shown in SEQ ID NO:2.
2. according to claim 1 heat endurance carbonic anhydrase at catalysis By Amine Solutions cyclic absorption-desorb CO
2in application, it is characterized in that, described heat endurance carbonic anhydrase is at catalysis By Amine Solutions cyclic absorption-desorb CO
2the method of middle application is comprise the steps:
(1) in the reactor that By Amine Solutions is housed, add the enzyme liquid of described carbonic anhydrase, addition is 15-75mL/L By Amine Solutions, and the weight weighing mixed solution in reactor is M0, at 25-40 DEG C, pass into CO in the mixed solution of described reactor
2, stir, detect pH, during no longer change stable to pH value, By Amine Solutions being weighed as to M1 and measuring volume is V1;
(2) absorption terminates rear rising temperature of reactor and starts desorb CO to 50-100 DEG C
2, stir, detect pH change, during pH value rising about 1.0, desorption process terminates, and measuring volume to By Amine Solutions is V2;
(3) if V1 is greater than V2, then add water to V1 volume to the By Amine Solutions in step (2), then, to the By Amine Solutions after step (2) desorb maybe this By Amine Solutions having added water be weighed as M2;
(4) in described cyclic absorption-desorb, the amount of the carbon dioxide of absorption is M1-M0, and after absorbing, Desorption of Carbon Dioxide amount is M1-M2;
(5) By Amine Solutions after step (3) desorb is down to room temperature, is recycled to the absorbing liquid that reactor absorbed as next time, repeat step (1)-(5), so circulate.
3. according to claim 1 heat endurance carbonic anhydrase at catalysis By Amine Solutions cyclic absorption-desorb CO
2in application, it is characterized in that, described By Amine Solutions is selected from the one in monoethanolamine, diethanol amine, methyl diethanolamine, triethanolamine, piperazine.
4. according to claim 2 heat endurance carbonic anhydrase at catalysis By Amine Solutions cyclic absorption-desorb CO
2in application, it is characterized in that, in described step (1) every 5-20min detect pH.
5. according to claim 2 heat endurance carbonic anhydrase at catalysis By Amine Solutions cyclic absorption-desorb CO
2in application, it is characterized in that, in described step (2) every 1-15min detect pH.
6. according to claim 2 heat endurance carbonic anhydrase at catalysis By Amine Solutions cyclic absorption-desorb CO
2in application, it is characterized in that, the detection of pH is measured at 27-28 DEG C in the described step (2).
7. according to claim 2 heat endurance carbonic anhydrase at catalysis By Amine Solutions cyclic absorption-desorb CO
2in application, it is characterized in that, the stir speed (S.S.) of described stirring is 200-450rpm.
8. according to claim 2 heat endurance carbonic anhydrase at catalysis By Amine Solutions cyclic absorption-desorb CO
2in application, it is characterized in that, the desorption time in described step (2) is 20-80min.
9. according to claim 1 heat endurance carbonic anhydrase at catalysis By Amine Solutions cyclic absorption-desorb CO
2in application, it is characterized in that, described heat endurance carbonic anhydrase is at catalysis By Amine Solutions cyclic absorption-desorb CO
23-8 time capable of circulation.
10. the nucleotide sequence as shown in SEQ ID NO:1 of a heat endurance carbonic anhydrase described in claim 1 of encoding.
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|---|---|---|---|---|
| CN107083408A (en) * | 2017-03-31 | 2017-08-22 | 昆明理工大学 | Carbonic anhydrase is in the application for being catalyzed in the conversion of carbon dioxide surfactant |
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