CN101054177B - Method and system for producing high concentration carbon dioxide of carbon-13 - Google Patents
Method and system for producing high concentration carbon dioxide of carbon-13 Download PDFInfo
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- CN101054177B CN101054177B CN2006100730847A CN200610073084A CN101054177B CN 101054177 B CN101054177 B CN 101054177B CN 2006100730847 A CN2006100730847 A CN 2006100730847A CN 200610073084 A CN200610073084 A CN 200610073084A CN 101054177 B CN101054177 B CN 101054177B
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Abstract
The present invention relates to a method and a system for preparing C-13 carbon dioxide with a high concentration, belonging to the preparing technical field of stable isotope C-13. The present invention discloses a method and system for the industrialized production of high concentration C-13; wherein the concentration of isotope is more than 99%, the natural carbon dioxide serves as raw material, the carbon dioxide/dinbutylamine/octane serves as the isotope exchange system, and a cold-hot refluxing method is adopted. In the present invention, the technical measures of raw gas presaturation, extractor segment and kettle liquid circulation are adopted, thereby the dosage of raw gas and the solvent consumption are reduced by 99% or so, and the concentration of the working solution of the system is stabilized, so that the concentration effect of the isotope is improved and the production cost is reduced. Furthermore, a hot reflux tower with a direct heat exchange-cool liquid leaching segment is adopted, and the operating temperature and the control requirement are reduced, thereby the crystallizing choking phenomenon is prevented, the operating is convenient and stable, and the energy consumption is saved.
Description
Technical field
The present invention relates to a kind of cold and hot backflow carbonic acid gas/Di-n-Butyl Amine/octane isotopic exchange and produce the method and system of high dense carbon-13, belong to stable isotope carbon-13 production technical field.
Background technology
Carbon in all carbonaceous materials of nature all is made up of two kinds of stable isotope carbon-12 and carbon-13, their natural content (title natural abundance) is respectively 98.99% and 1.01%, the atomic structure difference only is nuclear neutron number difference, and carbon-13 is than neutron more than the carbon-12.Because the outer character of their nuclear is identical, chemical property and most physical properties are identical, thus carbon-the 13rd, the tracer agent that carbon is best.Carbon is the main component of organic life entity, and carbon-the 13rd, stable isotope (promptly not having the radiological hazard problem), can be directly used in human body, so in scientific domains such as doctor, medicine, biological chemistry and life science, obtained using widely, had important economic and social benefit.
The prior art of suitability for industrialized production carbon-13 is-194 ℃ of carbon monoxide under low temperature rectificating methods, it is high that this method exists equipment, instrument to require, investment and energy consumption are bigger, need not only poison but also rare high-purity CO to do raw material, but also can not directly obtain the shortcomings such as carbon-13 product of 93% above concentration.
Summary of the invention
In order to overcome the shortcoming that prior art exists, reduce production costs, the invention provides a kind of method of producing high dense carbon-13 carbonic acid gas, this method is a raw material with a small amount of commercially available steel cylinder carbonic acid gas, with carbonic acid gas/Di-n-Butyl Amine/octane is carbon isotope exchange work system, cold and hot backflow by concentration section and these two workshop sections of extraction workshop section, the carbamate that makes carbonic acid gas and generate/octane solution generation carbon isotope exchange by Di-n-Butyl Amine/octane solution absorbing carbon dioxide, the process that the realization pump around circuit is separated carbon-12 and carbon-13;
1) concentration section
In concentration section, the hot reflux tower that extracts in the workshop section is decomposed carbonic acid gas that obtains and the raw material of thing as concentration section that conflux that has the carbonic acid gas of natural abundance on a small quantity, send into the 1st grade of cold reflux tower bottom of the 1st grade of upgrading tower top, flow from bottom to top, Di-n-Butyl Amine/octane solution the counter current contact that gets with being decomposed by the 1st grade of hot reflux tower in the 1st grade of upgrading tower below generates carbamate/octane solution; Allowing described carbamate/octane solution enter the 1st grade of upgrading tower cat head then flows from top to bottom, with carry out the isotope exchange reaction of carbon from the carbonic acid gas counter current contact of the 2nd grade of upgrading tower cat head, carbon-13 concentration constantly raises in feasible down mobile carbamate/octane solution, and carbon-13 concentration is constantly shelled light in the mobile carbonic acid gas that makes progress, flow out carbon-13 concentration the carbonic acid gas of described concentration section a little less than natural abundance from the 1st grade of upgrading tower cat head, with the raw material of this strand carbonic acid gas as extraction workshop section, deliver at the bottom of the tower that extracts the 1st grade of extraction column in the workshop section, continue to use, so that further extract carbon-13 wherein for isotope exchange reaction;
From the 1st grade of carbamate/octane solution that the upgrading tower tower bottom flow goes out, wherein carbon-13 concentration has obtained raising to a certain degree, allow it flow into the 1st hot reflux tower of the 1st grade of upgrading tower below, decomposes gets Di-n-Butyl Amine/octane solution and carbon-13 concentration obtains the to a certain degree carbonic acid gas of raising; Di-n-Butyl Amine/octane solution that described branch solves goes out from the 1st grade of hot reflux tower tower bottom flow, with the 1st grade of cold reflux column overhead in the 1st grade of upgrading tower top of metering pumped back, recycles behind water cooler; Described carbon-13 concentration obtains the carbonic acid gas that to a certain degree improves at the bottom of directly enter the 2nd grade of cold reflux Tata of the 2nd grade of upgrading tower top after the 1st grade of hot reflux tower cat head flows out, as the 2nd grade of raw material that concentrates carbon-13 later on of concentration section; So continue, the last level hot reflux tower cat head below the last level of concentration section upgrading tower obtains carbon-13 carbon dioxide product of required isotopes concentration;
In concentration section, the effusive absorption surplus carbon dioxide of each cold reflux column overhead is converged with the carbonic acid gas that the upgrading tower cat head of institute corresponding level comes out respectively, turn back to prime and concentrate at the bottom of the Tata, use for isotope exchange reaction;
2) extract workshop section
In extracting workshop section, Di-n-Butyl Amine/octane solution that the hot reflux tower tower bottom flow goes out in the workshop section will be extracted, behind water cooler, be pumped into cold reflux column overhead in the extraction workshop section with metering, flow from top to bottom, carbonic acid gas counter current contact with coming out from last level extraction column cat head generates carbamate/octane solution; Described carbamate/octane solution flows back to last level extraction column cat head again, identical with the upgrading tower principle of work, the same isotope exchange reaction that carbon takes place in described extraction column, gas phase is to the upper reaches, carbon-13 isotopes concentration constantly stripping is light, liquid phase is toward dirty, carbon-13 isotopes concentration improves gradually, directly all deliver to prime extraction column cat head from the liquid that the extraction column tower bottom flow goes out with volume pump, so continue, from the 1st grade of carbamate/octane solution that the extraction column tower bottom flow goes out, carbon wherein-13 isotopes concentration has returned to natural abundance, flow into the hot reflux tower that extracts workshop section, decompose the carbonic acid gas with natural abundance that obtains and be used as one of raw material sources of above-mentioned concentration section, it accounts for more than 99% of raw material total amount;
Flow out carbonic acid gas from the 1st grade of upgrading tower cat head of described concentration section, wherein carbon-13 concentration is a little less than natural abundance, with the raw material of this strand carbonic acid gas as extraction workshop section, deliver at the bottom of the 1st grade of extraction Tata that extracts in the workshop section, because the effect of carbon isotope permutoid reaction makes the 1st liquid phase carbon-13 isotopes concentration that extracts the Tata bottom return to natural abundance; Wherein carbon-13 isotopes concentration constantly descended during gas phase upwards flowed in extraction column, directly import at the bottom of the 2nd grade of extraction Tata after going out the 1st grade of extraction column cat head, continue light carbon-13 concentration wherein of stripping, so continue, in the end level extraction column cat head obtains the enough low carbonic acid gas of carbon-13 isotopes concentration, be carbon-12 carbonic acid gas, after the cold reflux tower in extracting workshop section absorbed and refluxes, superfluous sub-fraction was discharged after the washing constant voltage as tail gas.
After the described CO 2 raw material gas elder generation process wet with solvent with natural abundance that adds on a small quantity is saturated, again with extract hot reflux tower in the workshop section and decompose the carbonic acid gas that obtains and conflux the back as the raw material of concentration section, send into the 1st grade of cold reflux tower bottom of the 1st grade of upgrading tower top.
Described extraction column and the upgrading tower in the concentration section that extracts in the workshop section is adverse current gas-liquid mass transfer tower, and service temperature is 20～35 ℃, and working pressure is gauge pressure 0.01～0.03Mpa, and the liquid phase specific liquid rate is 0.5～5ml/cm
2.min.
At described concentrated cascade subsystem with extract in the scope that operation splitting temperature in the hot reflux tower of cascade subsystem is controlled in 60 ± 5 ℃.
The method of the invention comprises that also every fixed interval time carries out still liquid major cycle operation steps once, promptly last level hot reflux tower begins from concentration section, open the valve between last level thermal backflow Tata still and last the 2nd grade of thermal backflow Tata still, allowing the pressured difference of last level thermal backflow tower bottoms flow in last the 2nd grade of thermal backflow Tata still goes, treat that liquid level is reduced to down in limited time in the last level hot reflux tower, close described valve; Open the valve between last the 2nd grade of thermal backflow Tata still and the last 3rd level thermal backflow Tata still, allowing last the 2nd grade of pressured difference of thermal backflow tower bottoms flow in the last 3rd level thermal backflow Tata still goes, treat that liquid level drops to down in limited time in last the 2nd grade of thermal backflow Tata still, close described valve; By this operation, utilize still liquid recycle pump will extract workshop section's thermal backflow tower bottoms at last and send back in the last level of the concentration section thermal backflow Tata still successively, finish still liquid major cycle operation.
The method of the invention also is included in the still liquid branch road cyclical operation step of carrying out between any two thermal backflow Tata stills, promptly open the still liquid outlet stool valve of the hot reflux tower that needs extraction still liquid, open the still liquid inlet branch valve of the hot reflux tower that need pump into still liquid, start still liquid recycle pump simultaneously, according to two operated hot reflux tower level condition, the circulation of termination branch road, the termination of pumping closing valve is finished the cyclical operation of a still liquid branch road.
The present invention also provides a kind of system that produces high dense carbon-13 carbonic acid gas, comprises concentrating cascade subsystem, extraction cascade subsystem, raw material supply subsystem, and the washing tail gas pressurestat,
Described concentrated cascade subsystem comprises the multistage upgrading unit that connects by pipeline by cascade system, and every grade of upgrading unit includes
Upgrading tower,
By pipeline be communicated with described upgrading tower top the cold reflux tower,
The hot reflux tower that is communicated with described upgrading tower bottom by pipeline, and
Be located at described hot reflux tower bottom and lead to still liquid water cooler and volume pump on the liquid line of described cold reflux top of tower;
Described extraction cascade subsystem comprises
By the multistage extraction column of cascade system by the pipeline connection,
By gas and liquid line and the last grade of cold reflux tower that the extraction column top is communicated with,
The hot reflux tower that is communicated with the 1st grade of extraction column bottom by liquid line, and
Be located at described hot reflux tower bottom and lead to still liquid water cooler and volume pump on the liquid line of described cold reflux top of tower;
Described raw material supply subsystem comprises
Utilize the moistening unstripped gas presaturation tower of solvent saturation steam with carbonic acid gas of natural abundance, and
Be used for extracting the circulation volume pump that liquid is squeezed into unstripped gas presaturation column overhead out from described unstripped gas presaturation Tata still;
After the gas piping of unstripped gas presaturation column overhead merges in the gas piping at hot reflux tower top and the raw material supply subsystem in the described extraction cascade subsystem, be communicated with the bottom of the 1st grade of cold reflux tower in the described concentrated cascade subsystem by gas piping again; After the gas piping at the gas piping of the 1st grade of cold reflux top of tower and the 1st grade of upgrading tower top merges in the described concentrated cascade subsystem, be communicated with the bottom of the 1st grade of extraction column in the described extraction cascade subsystem by gas piping again; Cold reflux top of tower in the described extraction cascade subsystem is communicated with described washing tail gas pressurestat by gas piping.
Described concentrated cascade subsystem and the cold reflux tower that extracts in the cascade subsystem are tubulation membrane type or tubulation filler adverse current gas-liquid mass transfer tower.
Described concentrated cascade subsystem and the hot reflux tower that extracts in the cascade subsystem mainly are made up of the uninsulated direct heat exchange-drip washing packing section that is positioned at hot reflux tower top, the thermolysis packing section of insulation that is positioned at the hot reflux tower middle part and tubulation heating tower still three parts that are positioned at the hot reflux tower bottom, described direct heat exchange-cool liquid drip washing packing section height is 200-500mm, described thermolysis packing section height is 500-900mm, also be provided with between described direct heat exchange-drip washing packing section and the thermolysis packing section be used for measuring and the control decomposition temperature 60 ± 5 ℃ temperature control element.
The tower still of the hot reflux tower in the described system all also is provided with still liquid and imports and exports, each thermal backflow tower bottoms in the described concentrated cascade subsystem is imported and exported and is connected in series step by step by pipeline, and in pipeline mounted valve, the outlet of the 1st grade of thermal backflow tower bottoms links to each other with thermal backflow tower bottoms import in the described extraction cascade subsystem by pipeline in the described concentrated cascade subsystem, and in pipeline mounted valve, the thermal backflow tower bottoms outlet of described extraction cascade subsystem links to each other with a still liquid inlet of circulating pump through valve by pipeline, and described still liquid outlet of circulating pump links to each other with the still liquid import of last level hot reflux tower in the described concentrated cascade subsystem by pipeline.
Also be provided with the still liquid inlet branch of configuration valve and the still liquid outlet stool of configuration valve between each thermal backflow Tata still in the described system; The top of described still liquid outlet stool all is connected on the connecting pipeline between the corresponding thermal backflow Tata still, and on the terminal tandem to of the described still liquid outlet stool still liquid outlet header, described still liquid outlet header receives on the described still liquid inlet of circulating pump pipe; The top of described still liquid inlet branch all is connected on the described still liquid outlet of circulating pump house steward, and the terminal of described still liquid inlet branch all is connected on the connecting pipeline between the corresponding thermal backflow Tata still.
Compared with prior art, the invention has the advantages that:
1) have the people to use carbonic acid gas/Di-n-Butyl Amine/triethylamine isotopic exchange system in the prior art, because the saturated vapor pressure of triethylamine is 5.63 times of octane, volatile, the loss amount of taking away with tail gas carbon dioxide is bigger, influences production cost; And the work system of the method for the invention adopts carbonic acid gas/Di-n-Butyl Amine/octane isotopic exchange system, greatly reduces production cost.
2) hot reflux tower structure formation of mainly being made up of the thermolysis packing section and tubulation heating kettle three parts of tubulation gas phase water cooler and insulation that adopts with prior art and 70 ± 1 ℃ operation splitting condition thereof contrast, adopt the operation splitting condition of hot reflux tower structure formation of the present invention and 60 ± 5 ℃ to have following advantage: (1) stops crystallization obstruction accident, processing ease and stable, (2) low cost, (3) energy efficient about 20%.
3) still liquid of the present invention major cycle has guaranteed that with still liquid branch road circulation technology the concentration of working solution is consistent in the system.Different working solution concentration correspondences different gas phase flows, it is big that working solution concentration becomes, it will increase in the systemic carbon dioxide gas scale of construction of cold reflux tower, after decomposing, hot reflux tower will increase the gas phase flow in extraction column or the upgrading tower, otherwise, working solution concentration has diminished, and the gas phase flow is just little.Though it is constant to control the liquid phase volume flow in the production process, if can not keep the steady concentration of working solution, the gas phase flow still can not stablized.And flow is the most important factor of separation of isotopes cascade process Optimizing operation, and instability of flow can have a strong impact on the separation of isotopes effect.Because of flow rate fluctuation influences the separation of isotopes effect, this is the fact that former studies person recognizes in the cascade unit operation process, but they do not solve this and influence the key issue that isotope exchange method successfully concentrates high dense carbon-13.Because solvent boiling point is lower than solute in the cycle operation solution, so the researchist thinks that solvent can leave system with tail gas carbon dioxide with the saturated vapor pressure form in the cascade unit operation process more, so think that all hot reflux tower tower bottoms positions can descend gradually, working solution concentration also only can raise gradually, therefore adopt the way of control hot reflux tower tower bottoms position, added solvent to the tower still discontinuously.The inventor finds from each tower working solution concentration of practical measurement, each tower working solution concentration is to be the tower that the has changing pattern that the tower that has descends that raises, and same hot reflux tower tower bottoms position also can have to rise the phenomenon of falling is arranged, not always to descend, the yet decline that in the tower still that liquid level descends there is working solution concentration is not must be to raise.Changing pattern in view of this reality, the present invention has taked described still liquid cyclical operation method, promptly under described extraction workshop section and two measures cooperations of described unstripped gas presaturation tower, reached and to have added solvent to each tower still, it is constant only to need can to keep systemic circulation working solution concentration to the additional a small amount of solvent of unstripped gas presaturation Tata still, not only stablized gas phase flow in the system, improved carbon-13 concentrated effect, and reduced expensive solvent-oil ratio significantly, thereby reach the purpose that reduces production costs significantly.
Description of drawings
Fig. 1 is the synoptic diagram of an exemplary embodiments of system of realizing high dense carbon-13 carbonic acid gas of production of the method for the invention.
Fig. 2 is the process flow diagram of the high dense carbon-13 of production of the present invention carbonic acid gas.
Fig. 3 is a still liquid circulation technology schematic flow sheet of the present invention.
Embodiment
Further specify the present invention below in conjunction with drawings and Examples.
Fig. 1 has shown an embodiment of the system of the high dense carbon-13 of production of the present invention carbonic acid gas.The system of the high dense carbon-13 of described production carbonic acid gas comprises the concentrated cascade subsystem 2 that is used for concentration section, the extraction cascade subsystem 1 that is used to extract workshop section, raw material supply subsystem 3, and washing tail gas pressurestat 4.
In the present embodiment, concentrate cascade subsystem 2 and comprise the n level upgrading unit that connects by pipeline by cascade system, n is a positive integer.Every grade of upgrading unit includes upgrading tower 212, and (other upgrading tower is labeled as 222 accordingly, 2 (n-1) 2,2n2), by pipeline be communicated with described upgrading tower top cold reflux tower 211 (other cold reflux tower is labeled as 221 accordingly, 2 (n-1) 1,2n1), (other hot reflux tower is labeled as 223 to the hot reflux tower 213 that is communicated with described upgrading tower bottom by pipeline accordingly, 2 (n-1) 3,2n3), and be located at described hot reflux tower bottom and lead to still liquid water cooler 214 on the liquid line of described cold reflux top of tower (other still liquid water cooler is labeled as 224 accordingly, 2 (n-1) 4,2n4) and volume pump 215 (other volume pump is labeled as 225 accordingly, 2 (n-1) 5,2n5).The tower diameter that concentrates each upgrading tower in the cascade subsystem 2 rises with carbon-13 concentration wherein and successively decreases.
In the present embodiment, extract cascade subsystem 1 and comprise the m level extraction column 112 that connects by pipeline by cascade system, 122 ... 1 (m-1) 2 and 1m2, m is a positive integer, be located at the volume pump 125 on the liquid line of above-mentioned cascade ... 1 (m-1) 5,1m5, the cold reflux tower 1m1 that is communicated with last level extraction column 1m2 top by gas and liquid line, the hot reflux tower 113 that is communicated with the 1st grade of extraction column 112 bottoms by liquid line, and be located at described hot reflux tower 113 bottoms and lead to still liquid water cooler 114 and volume pump 115 on the liquid line at described cold reflux tower 1m1 top.The tower diameter of described m level extraction column is identical, and equals the tower diameter of the 1st grade of upgrading tower 212 in the described concentrated cascade subsystem 2.
The cold reflux tower that concentrates cascade subsystem 2 and extract in the cascade subsystem 1 is tubulation membrane type or tubulation filler adverse current gas-liquid mass transfer tower, and service temperature is 20～35 ℃, and working pressure is gauge pressure 0.01～0.03Mpa, and the liquid phase specific liquid rate is 0.5～5ml/cm
2.min.Because it is exothermic process that Di-n-Butyl Amine/octane solution absorbing carbon dioxide generates the process of carbamate/octane solution, in time from the cold reflux tower, take the operation that described reaction heat is cold reflux tower key away, under the commercial production scale situation, cool off water jacket or built-in again spiral coil cooling tube form heat-obtaining, because of the not enough poor effect of heat interchanging area by outside the tower body; External water cooler must add power and complex structure in addition.Adopt tubulation membrane type of the present invention or tubulation filler adverse current gas-liquid mass transfer tower then can solve described technical problem, guaranteed that the cold reflux tower operates under the optimization state in the system, guaranteed the concentrated effect of system's carbon-13.
Extract in the cascade subsystem 1 that upgrading tower all is adverse current gas-liquid mass transfer towers in the extraction column and concentrated cascade subsystem 2, service temperature is 20～35 ℃, and working pressure is gauge pressure 0.01～0.03Mpa, and the liquid phase specific liquid rate is 0.5～5ml/cm
2.min.
Hot reflux tower in concentrated cascade subsystem 2 and the extraction cascade subsystem 1 is mainly by the uninsulated direct heat exchange-drip washing packing section that is positioned at hot reflux tower top, being positioned at the thermolysis packing section of insulation at hot reflux tower middle part and tubulation heating tower still three parts that are positioned at the hot reflux tower bottom forms, described direct heat exchange-cool liquid drip washing packing section height is 200-500mm, described thermolysis packing section height is 500-900mm, also be provided with between described direct heat exchange-drip washing packing section and the thermolysis packing section and be used for measuring and the control decomposition temperature (concentrates hot reflux tower 213 in the cascade subsystem 2 60 ± 5 ℃ temperature control element, 223,2 (n-1) 3, the temperature control element that 2n3 is provided with is labeled as 216 respectively accordingly, 226,2 (n-1) 6,2n6 extracts the temperature control element that hot reflux tower 113 is provided with in the cascade subsystem 1 and is labeled 116).
In the present embodiment, raw material supply subsystem 3 comprises and utilizes the moistening unstripped gas presaturation tower 33 with carbonic acid gas of natural abundance of solvent saturation steam, and is used for extracting the circulation volume pump 34 that liquid is squeezed into unstripped gas presaturation tower 33 cats head out from described unstripped gas presaturation tower 33 tower stills.Described raw material supply subsystem 3 also comprise be equipped with carbon-13 isotopes concentration be natural abundance the unstripped gas carbonic acid gas steel cylinder 31 and be used for carbonic acid gas buffer tank 32 to unstripped gas decompression.Unstripped gas presaturation tower 33 is packing towers that have than container at the bottom of the big tower, bed stuffing height is 2～6 meters, optimum value is 3～4 meters, the packing tower diameter is identical with the tower diameter of minimum upgrading tower in the concentrated cascade subsystem, the tower still is a solvent feed tank, the tower still links to each other with described circulation volume pump 34 imports, and 34 outlets of circulation volume pump link to each other with unstripped gas presaturation tower 33 cat head fluid inlets.Container is equipped with the solvent octane of isotopic exchange cycle operation solution at the bottom of unstripped gas presaturation tower 33 towers.
In the present embodiment, washing tail gas pressurestat 4 adopts does wet two-tube constant liquid-level type washing tail gas pressurestat, change the operating pressure that washing tail gas pressurestat height can change whole work system, fill tap water in the described washing tail gas pressurestat, adopt the interior liquid level of float-type liquid level controller retainer constant, tail gas disperses the bubbling discharging by the water layer of constant level, not only reaches the effect of stable system pressure but also play the effect of washing tail gas.
After the gas piping of unstripped gas presaturation tower 33 cats head merges in the gas piping at hot reflux tower top and the raw material supply subsystem 3 in the extraction cascade subsystem 1, be communicated with the bottom of the 1st grade of cold reflux tower 211 in the concentrated cascade subsystem 2 by gas piping again; After the gas piping at the gas piping at the 1st grade of cold reflux tower 211 tops and the 1st grade of upgrading tower 212 tops merges in the concentrated cascade subsystem 2, be communicated with the bottom of the 1st grade of extraction column 112 in the extraction cascade subsystem 1 by gas piping again; The cold reflux tower 1m1 top of extracting in the cascade subsystem 1 is communicated with washing tail gas pressurestat 4 by gas piping.
In the present embodiment, the tower still of the hot reflux tower in the described system all also is provided with the import and export of still liquid.As shown in Figure 3, the still liquid outlet that concentrates the last level hot reflux tower 2n3 in the cascade subsystem links to each other with last the 2nd grade of hot reflux tower 2 (n-1) 3 still liquid imports by valve 2n33, the outlet of last the 2nd grade of hot reflux tower 2 (n-1) 3 still liquid links to each other with last 3rd level hot reflux tower 2 (n-2) 3 still liquid imports by valve 2 (n-1) 33, the 2nd grade of hot reflux tower 223 still liquid outlet that concentrates in the cascade subsystem links to each other with the 213 still liquid imports of the 1st grade of hot reflux tower by valve 2233, the 1st grade of hot reflux tower 213 still liquid outlet that concentrates in the cascade subsystem links to each other with hot reflux tower 113 still liquid imports in the described extraction cascade subsystem by valve 2133, the hot reflux tower 113 still liquid outlet of extracting in the cascade subsystem then links to each other with 5 imports of still liquid recycle pump through valve 1133, and 5 outlets of still liquid recycle pump link to each other with last grade of hot reflux tower 2n3 still liquid import in the concentrated cascade subsystem through valve 2n35.
In the present embodiment, also be provided with the still liquid inlet branch of configuration valve and the still liquid outlet stool of configuration valve between each the thermal backflow Tata still in the described system.As shown in Figure 3, the hot reflux tower 113 still liquid outlet in described extraction cascade subsystem is adorned a hot reflux tower 113 still liquid outlet stools with valve 1133 pipelines are middle, and joins a valve 1134, and the terminal of still liquid outlet stool is received on the still liquid outlet header 51; Hot reflux tower 213 still liquid outlet in the described concentrated cascade subsystem is adorned a hot reflux tower 213 still liquid outlet stools with valve 2133 pipelines are middle, and joins a valve 2134, and the terminal of still liquid outlet stool is received on the still liquid outlet header 51; The outlet of hot reflux tower 223 still liquid is adorned a hot reflux tower 223 still liquid outlet stools with valve 2233 pipelines are middle, and joins a valve 2234, and the terminal of still liquid outlet stool is received on the still liquid outlet header 51; The outlet of hot reflux tower 2 (n-1) 3 still liquid is adorned a hot reflux tower 2 (n-1) 3 still liquid outlet stools with valve 2 (n-1) 33 pipelines are middle, and joins a valve 2 (n-1) 34, and the terminal of still liquid outlet stool is received on the still liquid outlet header 51; The outlet of hot reflux tower 2n3 still liquid is adorned a hot reflux tower 2n3 still liquid outlet stool with valve 2n33 pipeline is middle, and joins a valve 2n34, and the terminal of still liquid outlet stool is received on the still liquid outlet header of system 51.Adorn a hot reflux tower 113 still liquid inlet branchs in the middle of hot reflux tower 113 still liquid imports in described extraction cascade subsystem and valve 2133 pipelines, and join a valve 1135, the top of still liquid inlet branch is received on the still liquid intake header 52; Adorn a hot reflux tower 213 still liquid inlet branchs in the middle of hot reflux tower 213 still liquid imports in the described concentrated cascade subsystem and valve 2233 pipelines, and join a valve 2135, the top of still liquid inlet branch is received on the still liquid intake header 52; Adorn a hot reflux tower 223 still liquid inlet branchs in the middle of hot reflux tower 223 still liquid imports and valve 2333 pipelines, and join a valve 2235, the top of still liquid inlet branch is received on the still liquid outlet header 52; Adorn a hot reflux tower 2 (n-1) 3 still liquid inlet branchs in the middle of hot reflux tower 2 (n-1) 3 still liquid imports and the valve 2n33 pipeline, and join a valve 2 (n-1) 35, the top of still liquid inlet branch is received on the still liquid outlet header 52; Adorn a valve 2n35 between liquid import of hot reflux tower 2n3 still and the still liquid outlet header 52.
It is raw material with a small amount of commercially available steel cylinder carbonic acid gas that cold and hot backflow carbonic acid gas/Di-n-Butyl Amine of the present invention/octane isotopic exchange is produced high dense carbon-13 method, with carbonic acid gas/Di-n-Butyl Amine/octane is carbon isotope exchange work system, cold and hot backflow by concentration section and these two workshop sections of extraction workshop section, the carbamate that makes carbonic acid gas and generate/octane solution generation carbon isotope exchange by Di-n-Butyl Amine/octane solution absorbing carbon dioxide, the process that the realization pump around circuit is separated carbon-12 and carbon-13.Fig. 2 has shown the technical process of the method for the high dense carbon-13 of production of the present invention carbonic acid gas.
As shown in Figure 2, the unstripped gas carbonic acid gas enters carbonic acid gas buffer tank 32 from steel cylinder 31 behind reducing valve, incoming stock again gas presaturation tower 33, enter packing layer from bottom to top from described unstripped gas presaturation tower packing layer bottom, extract and squeeze into the octane counter current contact of unstripped gas presaturation tower 33 cats head at the bottom of unstripped gas presaturation tower 33 towers the container out with circulation volume pump 34, come out from unstripped gas presaturation tower 33 cats head by fully moistening saturated back, flow is F, the carbonic acid gas 1132 that returns to natural abundance with carbon-13 isotopes concentration from hot reflux tower 113 cats head that extract workshop section converges again, forms the feed streams 1101 to concentration section.Because the raw gas flow that adds system is discharged the exhaust flow of system no better than, but when leaving system, tail gas taken away the solvent saturation steam under the system operation temperature, the solvent loss amount of this part by by solvent fully moistening unstripped gas to bring system into be ideal, so the present invention has guaranteed the balance of system's quantity of solvent, guaranteed Di-n-Butyl Amine in the work system/octane solution steady concentration, guarantee isotopic exchange place and optimal state, thereby guaranteed the concentrated effect of carbon-13.The method of the invention adopt need not purification process commercially available steel cylinder carbonic acid gas be raw material, and consumption seldom, only for not extracting 1/110 of workshop section, not only can save a large amount of expense of raw materials, and can also reduce the solvent loss amount of being taken away with the saturated vapor pressure form by tail gas, can reduce the production operation expense.
1) concentration section
The raw material of described concentration section is that described extraction workshop section extraction column bottom hot reflux tower decomposes the carbonic acid gas that obtains and the feed streams 1101 of confluxing and getting of raw material steel cylinder carbonic acid gas, and carbon-13 isotopes concentration that described carbonic acid gas confluxes in the thing is a natural abundance.The feed streams 1101 of described concentration section is introduced at the bottom of the 1st grade of cold reflux tower 211 towers of concentration section, flow from bottom to top, with decomposing by the 1st grade of hot reflux tower in the 1st grade of upgrading tower 212 belows 213 Di-n-Butyl Amine/octane solution 2131 deliver to Di-n-Butyl Amine/octane solution 2111 counter current contact of the 1st grade of hot reflux tower 213 cats head through the 1st grade of still liquid water cooler 214 and the 1st grade of volume pump 215, generate carbamate/octane solution 2112.Described carbamate/octane solution 2112 flows into described the 1st grade of upgrading tower 212 cats head, flow from top to bottom, with the carbonic acid gas 2222 that comes out from the 2nd grade of upgrading tower 222 cats head and from the converging of superfluous carbonic acid gas 2213 that the 2nd grade of cold reflux tower 221 cats head come out flowing 2201 counter current contact, carry out the isotope exchange reaction of carbon, carbon-13 concentration constantly raises in feasible down mobile carbamate/octane solution, and the continuous stripping of carbon-13 concentration is light in the mobile carbonic acid gas that makes progress, and carbon-13 concentration from the 1st grade of effusive carbonic acid gas 2122 of upgrading tower 212 cats head is a little less than natural abundance.Described carbonic acid gas 2122 converges formation with the superfluous carbonic acid gas 2113 that comes out from the 1st grade of cold reflux tower 211 cats head and converges stream 2101, described carbon-13 concentration of stream in 2101 of converging is only a little less than natural abundance, carbon wherein-13 should be made further extraction and application, so converging stream 2101 is that " tail gas " is discharged from concentration section for described concentration section, and for described extraction workshop section, be " unstripped gas ", utilize the carbon isotope function of exchange of extracting workshop section further to extract carbon-13 wherein and send described concentration section back to.
From described the 1st grade of carbamate/octane solution 2121 that upgrading tower 212 tower bottom flows go out, wherein carbon-13 concentration has obtained raising to a certain degree, allow it flow into the 1st grade of hot reflux tower 213 of described the 1st grade of upgrading tower 212 belows, and the operation splitting temperature is in 60 ± 5 ℃ scope in the control hot reflux tower, and decomposes gets Di-n-Butyl Amine/octane solution 2131 and carbon-13 concentration obtains the to a certain degree carbonic acid gas 2132 of raising.Di-n-Butyl Amine/octane solution 2131 that described branch solves goes out from the 1st grade of hot reflux tower 213 tower bottom flows, sends the 1st grade of cold reflux tower 211 cats head of described the 1st grade of upgrading tower 212 tops behind the 1st grade of water cooler 214 back to the 1st grade of volume pump 215, recycles; Described carbon-13 concentration obtains the carbonic acid gas 2132 that to a certain degree improves at the bottom of directly enter the 2nd grade of cold reflux tower 221 towers of the 2nd grade of upgrading tower 222 tops of described concentration section after the 1st grade of hot reflux tower 213 cats head come out, as the 2nd grade of raw material that concentrates carbon-13 later on of described concentration section.So continue, can obtain the carbon-13 carbonic acid gas 2n32 of required isotopes concentration at last grade of hot reflux tower 2n3 cat head below the last level of the described concentration section upgrading tower 2n2, meet the requirements of from described carbon-13 isotopes concentration and take out sub-fraction the carbonic acid gas 2n32 as the synthetic system's (not being presented among Fig. 2) of product flow P importing labeling compound.
In concentration section, the effusive absorption surplus carbon dioxide of each cold reflux column overhead is converged with the carbonic acid gas that the upgrading tower cat head of institute corresponding level comes out respectively, turn back to prime and concentrate at the bottom of the Tata, use for isotope exchange reaction.
2) extract workshop section
Di-n-Butyl Amine/the octane solution 1131 that goes out from described extraction workshop section hot reflux tower 113 tower bottom flows, be cooled to room temperature through extracting workshop section's water cooler 114, deliver to the described extraction cold reflux tower 1m1 of workshop section cat head by obtaining Di-n-Butyl Amine/octane solution stream 1m11 after volume pump 115 meterings, flow from top to bottom, with the carbonic acid gas 1m22 counter current contact of coming out from the described last level extraction column 1m2 of extraction workshop section cat head, generate carbamate/octane solution 1m12, flow into the described last level extraction column 1m2 of extraction workshop section cat head.Logistics 1m21 behind the described extraction column 1m2 of outflow directly all delivers to prime extraction column 1 (m-1) 2 cats head with volume pump 1m5 downwards, identical with the upgrading tower principle of work, the same isotope exchange reaction that carbon takes place in described extraction column, gas phase is to the upper reaches, carbon-13 isotopes concentration constantly stripping is light, liquid phase is toward dirty, carbon-13 isotopes concentration improves gradually, so continue, carbamate/the octane solution 1121 that goes out from the 1st grade of extraction column 112 tower bottom flows, carbon wherein-13 isotopes concentration has returned to natural abundance, flow into described extraction workshop section hot reflux tower 113, and in the control hot reflux tower operation splitting temperature in 60 ± 5 ℃ scope, the carbonic acid gas 1132 that decomposition obtains wherein carbon-13 isotopes concentration is natural abundance, therefore can replace most feed carbon dioxide gases (accounting for more than 99% of raw material total amount), converge to form with the CO 2 raw material gas F of a small amount of reality and converge stream 1101, add at the bottom of the 1st grade of cold reflux tower 211 towers of described concentration section, as the raw material use of described concentration section.
" tail gas " 2101 that gives off from described concentration section, wherein carbon-13 concentration is a little less than natural abundance, with the raw material of this strand carbonic acid gas as described extraction workshop section, deliver at the bottom of the 1st grade of extraction column 112 towers that extract in the workshop section, because the effect of carbon isotope permutoid reaction makes liquid phase carbon-13 isotopes concentration of described the 1st grade of extraction column 112 tower bottoms return to natural abundance.Wherein carbon-13 isotopes concentration constantly descended during gas phase upwards flowed in extraction column, directly import at the bottom of the 2nd grade of extraction column 122 towers after going out described the 1st grade of extraction column 112 cats head, continue light carbon-13 concentration wherein of stripping, so continue and to obtain the enough low carbonic acid gas 1m22 (being carbon-12 carbonic acid gas) of carbon-13 isotopes concentration at the described last level extraction column 1m2 of extraction workshop section cat head, after the described extraction cold reflux tower 1m1 of workshop section absorbs backflow, superfluous sub-fraction 1m13 (quantitatively equals actual CO 2 material flow amount F and deducts product flow P, actual no better than CO 2 material flow amount) as tail gas W outside washing tail gas pressurestat 4 discharge systems, utilize tap water 41 and be installed in washing tail gas pressurestat 4 wet floating ball type water level controllers of managing tops, at any time replenish the current of being taken away with saturation steam form under the room temperature by tail gas, it is constant to keep washing tail gas pressurestat 4 interior liquid levels.
Fig. 3 has shown still liquid circulation technology flow process of the present invention.Still liquid circulation technology comprises the major cycle of still liquid and two technological processs of still liquid branch road circulation.
Still liquid major cycle technology, just every fixed interval time is carried out still liquid major cycle operation once, concrete steps are: the last level hot reflux tower 2n3 from concentration section begins, open valve 2n33, allowing the pressured difference of last level hot reflux tower 2n3 still liquid flow in the tower still of last the 2nd grade of hot reflux tower 2 (n-1) 3 goes, treat that level hot reflux tower 2n3 liquid level is reduced to down in limited time valve-off 2n33 at last; Open the valve 2 (n-1) 33 between last the 2nd grade of hot reflux tower 2 (n-1) 3 tower stills and last 3rd level hot reflux tower 2 (n-2) the 3 tower stills, allowing the pressured difference of last the 2nd grade of hot reflux tower 2 (n-1) 3 still liquid flow in the tower still of last 3rd level hot reflux tower 2 (n-2) 3 goes, treat that liquid level drops to down in limited time in last the 2nd grade of hot reflux tower 2 (n-1) the 3 tower stills, valve-off 2 (n-1) 33; Successively by this operation, the hot reflux tower 113 still liquid that utilize still liquid recycle pump 5 will extract in the workshop section at last go in valve 2n35 sends the tower still of the last level hot reflux tower 2n3 in the concentration section back to, finish a still liquid major cycle and operate.
Still liquid branch road circulation technology, the still liquid branch road cyclical operation of between any two thermal backflow Tata stills, carrying out just, concrete steps are: open hot reflux tower (as 213) the still liquid outlet stool valve (as 2134) that needs to extract out still liquid, open hot reflux tower [as 2 (n-1) 3] the still liquid inlet branch valve [as 2 (n-1) 35] that need pump into still liquid, start still liquid recycle pump 5 simultaneously, according to two operated hot reflux tower level condition, the circulation of termination branch road, the termination of pumping closing valve can be finished the cyclical operation of a still liquid branch road.
Below, describe a specific embodiment of system of the present invention and produce the processing parameter of high dense carbon-13 carbonic acid gas in the tabulation mode.With carbon-13 natural abundance is that 1.1% commercially available steel cylinder carbonic acid gas is a raw material, uses 10 grades of upgrading towers in concentration section, uses 2 extraction columns in extracting workshop section, produces the carbonic acid gas (wherein carbon-13 isotopes concentration 〉=99%) of 1000 gram clean carbon-13 per year.
(1) basic parameter:
`
(2) major equipment parameter:
1. tubulation filler tower cold reflux tower significant parameter [mm]:
| Title and numbering | Structural summary | The tubulation internal diameter | The filler height | Filling kind |
| Extract the cold reflux tower B# of workshop section | 91 tubulations, the shell side water coolant | 40 | 1200 | Small-sized dumped packing |
| Concentration section cold reflux tower 1# | 91 tubulations, the shell side water coolant | 40 | 1200 | Small-sized dumped packing |
| Concentration section cold reflux tower 2# | 91 tubulations, the shell side water coolant | 32 | 1200 | Small-sized dumped packing |
| Concentration section cold reflux tower 3# | 61 tubulations, the shell side water coolant | 40 | 1200 | Small-sized dumped packing |
| Concentration section cold reflux tower 4# | 61 tubulations, the shell side water coolant | 32 | 1200 | Small-sized dumped packing |
| Concentration section cold reflux tower 5# | 61 tubulations, the shell side water coolant | 28 | 1200 | Small-sized dumped packing |
| Concentration section cold reflux tower 6# | 61 tubulations, the shell side water coolant | 25 | 1200 | Small-sized dumped packing |
| Concentration section cold reflux tower 7# | 35 tubulations, the shell side water coolant | 25 | 1200 | Small-sized dumped packing |
| Concentration section cold reflux tower 8# | 7 tubulations, the shell side water coolant | 28 | 1200 | Small-sized dumped packing |
| Concentration section cold reflux tower 9# | 7 tubulations, the shell side water coolant | 25 | 1200 | Small-sized dumped packing |
| Concentration section cold reflux tower | 7 tubulations, the shell side water coolant | 25 | 1200 | Small-sized dumped packing |
2. filler tower isotopic exchange tower significant parameter [mm]:
| Title and numbering | The filler material | Filling kind | The tower internal diameter | Bed stuffing height |
| The 2nd extraction column B# | The 304# Stainless Steel Wire | Structured packing | 300 | 16000 |
| The 1st extraction column A# | The 304# Stainless Steel Wire | Structured packing | 300 | 16000 |
| The |
The 304# Stainless Steel Wire | Structured packing | 300 | 16000 |
| The |
The 304# Stainless Steel Wire | Structured packing | 280 | 16000 |
| The 3rd upgrading tower 3# | The 304# Stainless Steel Wire | Structured packing | 240 | 16000 |
| The |
The 304# Stainless Steel Wire | Structured packing | 200 | 16000 |
| The |
The 304# Stainless Steel Wire | Structured packing | 180 | 16000 |
| The |
The 304# Stainless Steel Wire | Dumped packing | 150 | 16000 |
| The 7th upgrading tower 7# | The 304# Stainless Steel Wire | Random packing | 100 | 16000 |
| The 8th upgrading tower 8# | The 304# Stainless Steel Wire | Random packing | 60 | 16000 |
| The 9th upgrading tower 9# | The 304# Stainless Steel Wire | Random packing | 50 | 16000 |
| The 10th upgrading tower 10# | The 304# Stainless Steel Wire | Random packing | 50 | 16000 |
3. hot reflux tower significant parameter:
Each tower direct heat exchange-washing section bed stuffing height is 0.4m, decomposes the section bed stuffing height and is 0.7m, and two sections tower diameters are identical, all use the structured packing of 304# Stainless Steel Cloth system.
| Title and numbering | Packing tower internal diameter [mm] | Heating tower's still pattern |
| Extract the hot reflux tower A# of workshop section | 330 | |
| Concentration section |
330 | Shell-and-tube, tube side material, shell side heating steam |
| Concentration section |
300 | Shell-and-tube, tube side material, shell side heating steam |
| Concentration section hot reflux tower 3# | 270 | Shell-and-tube, tube side material, shell side heating steam |
| Concentration section |
220 | Shell-and-tube, tube side material, shell side heating steam |
| Concentration section |
200 | Shell-and-tube, tube side material, shell side heating steam |
| Concentration section |
170 | Shell-and-tube, tube side material, shell side heating steam |
| Concentration section hot reflux tower 7# | 110 | Shell-and-tube, tube side material, shell side heating steam |
| Concentration section hot reflux tower 8# | 60 | Shell-and-tube, tube side material, shell side heating steam |
| Concentration section hot reflux tower 9# | 55 | Shell-and-tube, tube side material, shell side heating steam |
| Concentration section hot reflux tower 10# | 55 | Shell-and-tube, tube side material, shell side heating steam |
(3) isotopic exchange tower flow:
| The logistics title | Unit | Flow |
| Extraction column B#, A# vapour phase flow | l/min | 64.54 |
| Extraction column B#, A# liquid phase flow | ml/min | 2380 |
| |
l/min | 64.59 |
| |
ml/min | 2403 |
| |
l/min | 49.97 |
| |
ml/min | 1859 |
| Upgrading tower 3# vapour phase flow | l/min | 37.83 |
| Upgrading tower 3# liquid phase flow | ml/min | 1407 |
| |
l/min | 28.46 |
| |
ml/min | 1059 |
| |
l/min | 20.98 |
| |
ml/min | 781 |
| |
l/min | 15.42 |
| |
ml/min | 574 |
| Upgrading tower 7# vapour phase flow | l/min | 6.11 |
| Upgrading tower 7# liquid phase flow | ml/min | 227 |
| Upgrading tower 8# vapour phase flow | l/min | 2.55 |
| Upgrading tower 8# liquid phase flow | ml/min | 95.0 |
| Upgrading tower 9# vapour phase flow | l/min | 1.60 |
| Upgrading tower 9# liquid phase flow | ml/min | 59.5 |
| Upgrading tower 10# vapour phase flow | l/min | 0.98 |
| Upgrading tower 10# liquid phase flow | ml/min | 36.5 |
(4) carbon-13 isotropic substance concentrates the result:
Claims (8)
1. method of producing high dense carbon-13 carbonic acid gas, it is characterized in that: this method is a raw material with a small amount of commercially available steel cylinder carbonic acid gas, with carbonic acid gas/Di-n-Butyl Amine/octane is carbon isotope exchange work system, cold and hot backflow by concentration section and these two workshop sections of extraction workshop section, the carbamate that makes carbonic acid gas and generate/octane solution generation carbon isotope exchange by Di-n-Butyl Amine/octane solution absorbing carbon dioxide, the process that the realization pump around circuit is separated carbon-12 and carbon-13;
1) concentration section
In concentration section, the hot reflux tower that extracts in the workshop section is decomposed carbonic acid gas that obtains and the raw material of thing as concentration section that conflux that has the carbonic acid gas of natural abundance on a small quantity, send into the 1st grade of cold reflux tower bottom of the 1st grade of upgrading tower top, flow from bottom to top, Di-n-Butyl Amine/octane solution the counter current contact that gets with being decomposed by the 1st grade of hot reflux tower in the 1st grade of upgrading tower below generates carbamate/octane solution; Allowing described carbamate/octane solution enter the 1st grade of upgrading tower cat head then flows from top to bottom, with carry out the isotope exchange reaction of carbon from the carbonic acid gas counter current contact of the 2nd grade of upgrading tower cat head, carbon-13 concentration constantly raises in feasible down mobile carbamate/octane solution, and carbon-13 concentration is constantly shelled light in the mobile carbonic acid gas that makes progress, flow out carbon-13 concentration the carbonic acid gas of described concentration section a little less than natural abundance from the 1st grade of upgrading tower cat head, with the raw material of this strand carbonic acid gas as extraction workshop section, deliver at the bottom of the tower that extracts the 1st grade of extraction column in the workshop section, continue to use, so that further extract carbon-13 wherein for isotope exchange reaction;
From the 1st grade of carbamate/octane solution that the upgrading tower tower bottom flow goes out, wherein carbon-13 concentration has obtained raising to a certain degree, allow it flow into the 1st hot reflux tower of the 1st grade of upgrading tower below, decomposes gets Di-n-Butyl Amine/octane solution and carbon-13 concentration obtains the to a certain degree carbonic acid gas of raising; Di-n-Butyl Amine/octane solution that described branch solves goes out from the 1st grade of hot reflux tower tower bottom flow, with the 1st grade of cold reflux column overhead in the 1st grade of upgrading tower top of metering pumped back, recycles behind water cooler; Described carbon-13 concentration obtains the carbonic acid gas that to a certain degree improves at the bottom of directly enter the 2nd grade of cold reflux Tata of the 2nd grade of upgrading tower top after the 1st grade of hot reflux tower cat head flows out, as the 2nd grade of raw material that concentrates carbon-13 later on of concentration section; So continue, the last level hot reflux tower cat head below the last level of concentration section upgrading tower obtains carbon-13 carbon dioxide product of required isotopes concentration;
In concentration section, the effusive absorption surplus carbon dioxide of each cold reflux column overhead is converged with the carbonic acid gas that the upgrading tower cat head of institute corresponding level comes out respectively, turn back to prime and concentrate at the bottom of the Tata, use for isotope exchange reaction;
2) extract workshop section
In extracting workshop section, Di-n-Butyl Amine/octane solution that the hot reflux tower tower bottom flow goes out in the workshop section will be extracted, behind water cooler, be pumped into cold reflux column overhead in the extraction workshop section with metering, flow from top to bottom, carbonic acid gas counter current contact with coming out from last level extraction column cat head generates carbamate/octane solution; Described carbamate/octane solution flows back to last level extraction column cat head again, identical with the upgrading tower principle of work, the same isotope exchange reaction that carbon takes place in described extraction column, gas phase is to the upper reaches, carbon-13 isotopes concentration constantly stripping is light, liquid phase is toward dirty, carbon-13 isotopes concentration improves gradually, directly all deliver to prime extraction column cat head from the liquid that the extraction column tower bottom flow goes out with volume pump, so continue, from the 1st grade of carbamate/octane solution that the extraction column tower bottom flow goes out, carbon wherein-13 isotopes concentration has returned to natural abundance, flow into the hot reflux tower that extracts workshop section, decompose the carbonic acid gas with natural abundance that obtains and be used as one of raw material sources of above-mentioned concentration section, it accounts for more than 99% of raw material total amount;
Flow out carbonic acid gas from the 1st grade of upgrading tower cat head of described concentration section, wherein carbon-13 concentration is a little less than natural abundance, with the raw material of this strand carbonic acid gas as extraction workshop section, deliver at the bottom of the 1st grade of extraction Tata that extracts in the workshop section, because the effect of carbon isotope permutoid reaction makes the 1st liquid phase carbon-13 isotopes concentration that extracts the Tata bottom return to natural abundance; Wherein carbon-13 isotopes concentration constantly descended during gas phase upwards flowed in extraction column, directly import at the bottom of the 2nd grade of extraction Tata after going out the 1st grade of extraction column cat head, continue light carbon-13 concentration wherein of stripping, so continue, in the end level extraction column cat head obtains the enough low carbonic acid gas of carbon-13 isotopes concentration, be carbon-12 carbonic acid gas, after the cold reflux tower in extracting workshop section absorbed and refluxes, superfluous sub-fraction was discharged after the washing constant voltage as tail gas;
Described method comprises that also every fixed interval time carries out still liquid major cycle operation steps once, promptly last level hot reflux tower begins from concentration section, open the valve between last level thermal backflow Tata still and last the 2nd grade of thermal backflow Tata still, allowing the pressured difference of last level thermal backflow tower bottoms flow in last the 2nd grade of thermal backflow Tata still goes, treat that liquid level is reduced to down in limited time in the last level hot reflux tower, close described valve; Open the valve between last the 2nd grade of thermal backflow Tata still and the last 3rd level thermal backflow Tata still, allowing last the 2nd grade of pressured difference of thermal backflow tower bottoms flow in the last 3rd level thermal backflow Tata still goes, treat that liquid level drops to down in limited time in last the 2nd grade of thermal backflow Tata still, close described valve; By this operation, utilize still liquid recycle pump will extract workshop section's thermal backflow tower bottoms at last and send back in the last level of the concentration section thermal backflow Tata still successively, finish still liquid major cycle operation;
Described method also is included in the still liquid branch road cyclical operation step of carrying out between any two thermal backflow Tata stills, promptly open the still liquid outlet stool valve of the hot reflux tower that needs extraction still liquid, open the still liquid inlet branch valve of the hot reflux tower that need pump into still liquid, start still liquid recycle pump simultaneously, according to two operated hot reflux tower level condition, the circulation of termination branch road, the termination of pumping closing valve is finished the cyclical operation of a still liquid branch road.
2. the method for the high dense carbon-13 of production according to claim 1 carbonic acid gas, it is characterized in that: after the described CO 2 raw material gas elder generation process wet with solvent with natural abundance that adds on a small quantity is saturated, again with extract hot reflux tower in the workshop section and decompose the carbonic acid gas that obtains and conflux the back as the raw material of concentration section, send into the 1st grade of cold reflux tower bottom of the 1st grade of upgrading tower top.
3. the method for the high dense carbon-13 of production according to claim 1 carbonic acid gas, it is characterized in that: described extraction column and the upgrading tower in the concentration section that extracts in the workshop section is adverse current gas-liquid mass transfer tower, service temperature is 20～35 ℃, working pressure is gauge pressure 0.01～0.03MPa, and the liquid phase specific liquid rate is 0.5～5ml/cm
2.min.
4. the method for the high dense carbon-13 of production according to claim 1 carbonic acid gas is characterized in that: at described concentrated cascade subsystem with extract in the scope that operation splitting temperature in the hot reflux tower of cascade subsystem is controlled in 60 ± 5 ℃.
5. system that produces high dense carbon-13 carbonic acid gas is characterized in that: described system comprises and concentrates the cascade subsystem, extracts cascade subsystem, raw material supply subsystem, and the washing tail gas pressurestat,
Described concentrated cascade subsystem comprises the multistage upgrading unit that connects by pipeline by cascade system, and every grade of upgrading unit includes
Upgrading tower,
By pipeline be communicated with described upgrading tower top the cold reflux tower,
The hot reflux tower that is communicated with described upgrading tower bottom by pipeline, and
Be located at described hot reflux tower bottom and lead to still liquid water cooler and volume pump on the liquid line of described cold reflux top of tower;
Described extraction cascade subsystem comprises
By the multistage extraction column of cascade system by the pipeline connection,
By gas and liquid line and the last grade of cold reflux tower that the extraction column top is communicated with,
The hot reflux tower that is communicated with the 1st grade of extraction column bottom by liquid line, and
Be located at described hot reflux tower bottom and lead to still liquid water cooler and volume pump on the liquid line of described cold reflux top of tower;
Described raw material supply subsystem comprises
Utilize the moistening unstripped gas presaturation tower of solvent saturation steam with carbonic acid gas of natural abundance, and
Be used for extracting the circulation volume pump that liquid is squeezed into unstripped gas presaturation column overhead out from described unstripped gas presaturation Tata still;
After the gas piping of unstripped gas presaturation column overhead merges in the gas piping at hot reflux tower top and the raw material supply subsystem in the described extraction cascade subsystem, be communicated with the bottom of the 1st grade of cold reflux tower in the described concentrated cascade subsystem by gas piping again; After the gas piping at the gas piping of the 1st grade of cold reflux top of tower and the 1st grade of upgrading tower top merges in the described concentrated cascade subsystem, be communicated with the bottom of the 1st grade of extraction column in the described extraction cascade subsystem by gas piping again; Cold reflux top of tower in the described extraction cascade subsystem is communicated with described washing tail gas pressurestat by gas piping;
The tower still of the hot reflux tower in the described system all also is provided with still liquid and imports and exports, each thermal backflow tower bottoms in the described concentrated cascade subsystem is imported and exported and is connected in series step by step by pipeline, and in pipeline mounted valve, the outlet of the 1st grade of thermal backflow tower bottoms links to each other with thermal backflow tower bottoms import in the described extraction cascade subsystem by pipeline in the described concentrated cascade subsystem, and in pipeline mounted valve, the thermal backflow tower bottoms outlet of described extraction cascade subsystem links to each other with a still liquid inlet of circulating pump through valve by pipeline, and described still liquid outlet of circulating pump links to each other with the still liquid import of last level hot reflux tower in the described concentrated cascade subsystem by pipeline;
Also be provided with the still liquid inlet branch of configuration valve and the still liquid outlet stool of configuration valve between each thermal backflow Tata still in the described system; The top of described still liquid outlet stool all is connected on the connecting pipeline between the corresponding thermal backflow Tata still, and on the terminal tandem to of the described still liquid outlet stool still liquid outlet header, described still liquid outlet header receives on the described still liquid inlet of circulating pump pipe; The top of described still liquid inlet branch all is connected on the described still liquid outlet of circulating pump house steward, and the terminal of described still liquid inlet branch all is connected on the connecting pipeline between the corresponding thermal backflow Tata still.
6. the system of the high dense carbon-13 of production according to claim 5 carbonic acid gas is characterized in that: described concentrated cascade subsystem and the cold reflux tower that extracts in the cascade subsystem are tubulation membrane type or tubulation filler adverse current gas-liquid mass transfer tower.
7. the system of the high dense carbon-13 of production according to claim 5 carbonic acid gas, it is characterized in that: the hot reflux tower in described concentrated cascade subsystem and the extraction cascade subsystem is mainly by the uninsulated direct heat exchange-drip washing packing section that is positioned at hot reflux tower top, being positioned at the thermolysis packing section of insulation at hot reflux tower middle part and tubulation heating tower still three parts that are positioned at the hot reflux tower bottom forms, described direct heat exchange-cool liquid drip washing packing section height is 200-500mm, described thermolysis packing section height is 500-900mm, also be provided with between described direct heat exchange-drip washing packing section and the thermolysis packing section be used for measuring and the control decomposition temperature 60 ± 5 ℃ temperature control element.
8. the system of the high dense carbon-13 of production according to claim 5 carbonic acid gas is characterized in that: described washing tail gas pressurestat is for doing wet two-tube constant liquid-level type washing tail gas pressurestat.
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| CN2897991Y (en) * | 2006-04-13 | 2007-05-09 | 杨国华 | System for producing high-concentration carbon-13-carbon dioxide |
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