CN108525463A - A kind of CO2/CH4CO in mixed gas2Separation method - Google Patents
A kind of CO2/CH4CO in mixed gas2Separation method Download PDFInfo
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Abstract
The invention discloses a kind of CO2/CH4CO in mixed gas2Separation method, include the following steps：The drying of activated carbon；Dry activated carbon and the mixed modification of 2 methylimidazoles, ethylene glycol, ethyl alcohol；Modified activated carbon is in sapphire kettle to containing CO under specified conditions2/CH4CO in gaseous mixture2Adsorbing separation；Modified activated carbon is calculated to CO2Adsorbance and to CO2/CH4The separation factor of gaseous mixture.The present invention loads 2 methylimidazoles, ethyl alcohol and ethylene glycol in activated carbon surface, and the hydroxyl in 2 methylimidazole molecules in the ethyl alcohol of N atoms and activated carbon surface, glycol molecule is made to form hydrogen bond, forms film in activated carbon surface, hinders to CH4The absorption of molecule；Meanwhile CO2Molecule reacted with 2 methylimidazoles to be formed include N C keys carbamate, improve activated carbon to CO2Adsorptive selectivity, to substantially increase activated carbon to CO2/CH4The separating effect of gaseous mixture.
Description
Technical field
The invention belongs to gas separation technique fields, and in particular to a kind of CO2/CH4CO in mixed gas2Separation method.
Background technology
With the development of economy and society, the consumption of coal and oil is growing day by day, thing followed environmental problem is also increasingly
Prominent, people are highly desirable to find a kind of environmental-friendly fungible energy source.Natural gas is as a kind of high-quality clean energy resource, with it
He compares fuel, has the advantages that convenience, economy, calorific value are high, pollution is few, and natural gas as fuel energy effectively reduce CO,
CO2、NOXAnd the discharge of hydro carbons etc., be conducive to environmental protection.The main component of natural gas is generally CH4And CO2, wherein CO2's
In the presence of but bringing many hazards：CO2For sour gas, meets water and be easy to be formed acid solution and corrosion pipeline equipment；It reduces natural
The calorific value of gas；Low temperature easily forms hydrate, to block natural gas transportation pipeline etc..
Currently, industrially removing the CO in natural gas2Mainly use chemical absorption method, wherein hydramine is molten with alcamines
Agent such as ethanol amine, diethanol amine etc. is absorbent, due to absorption efficiency is high, technical maturity and be used widely, but due to
There are the absorption/regeneration temperature difference big, solvent reclamation high energy consumption, equipment burn into amine high temperature degradation and it is volatile the shortcomings of, the method
It reapplies and is somewhat limited.
Absorption method is also a kind of good CO removed in natural gas2Method, porous material absorption partition method is to containing
CO2It occupies a tiny space in the method that gaseous mixture is detached.Since Activated Carbon Production is at low cost, purchase channel is wide, therefore, living
Property charcoal be the porous material considered first using adsorption separation method.But more other porous materials (such as MOFs) are compared, activity
Charcoal is to CH4And CO2Simultaneously apparent advantage is not present in the separating effect of gaseous mixture, and therefore, researchers are from many aspects to activated carbon
Separating property improved, such as：Activated carbon fibre, activated charcoal membrane inject polyethyleneimine synthesis carbon molecules in activated carbon
Sieve adsorbant etc., but these methods are either of high cost or complicated for operation or to CH4And CO2The separating effect of gaseous mixture
And it is bad, therefore, urgent need improves the prior art, to find a kind of new adsorbent, realizes significantly more efficient separation CH4
And CO2CO in gaseous mixture2Absorption method.
Invention content
The present invention provides a kind of CO2/CH4CO in mixed gas2Separation method, solve useization in the prior art
It learns absorption process and detaches CO2There are many restrictions, and uses absorption method separation then either there are of high cost or to there is operation multiple
Miscellaneous or presence is to CH4And CO2The separating effect of gaseous mixture and bad problem.
The present invention provides a kind of CO2/CH4CO in mixed gas2Separation method, include the following steps：
Step 1, under vacuum, by activated carbon, drying for 24 hours, is cooled to room temperature after dry, obtains at 120 DEG C
Dry activated carbon；
Step 2, by 2-methylimidazole, ethylene glycol, ethyl alcohol according to 1.01：1.64：10 mass ratio is uniformly mixed, and is mixed
Close solution；
By the dry activated carbon obtained in step 1 and the mixed solution according to 3.3：12.65 mass ratio mixing, obtains
Solidliquid mixture；
Step 3, solidliquid mixture in step 2 is stood one week under vacuum, it is then dry at 80 DEG C, and dry
It is dry during monitoring activated carbon in ethyl alcohol hole hold occupation rate, when monitor ethyl alcohol in activated carbon hole hold occupation rate reach 10%
When above, that is, terminate drying, obtains modified activated carbon；
Step 4, modified activated carbon in step 3 is placed in sapphire kettle, sapphire kettle with valvular pipeline by connecting
It is connected with equilibrium still, sapphire kettle and the valve on equilibrium still connecting pipeline is closed, equilibrium still and its institute's connecting leg road is vacuumized, waited for
After air drains in equilibrium still and its institute's connecting leg road, by CO2/CH4Mixed gas is squeezed into equilibrium still
3.70MPa；
Temperature control is carried out to sapphire kettle, when sapphire temperature in the kettle stablizes the pressure stability in 10 DEG C and equilibrium still, note
Record the pressure reading of equilibrium still；Sapphire kettle and its institute's connecting leg road are vacuumized simultaneously, waited in sapphire kettle and its institute's connecting leg road
After air drains, the valve on connecting pipeline between equilibrium still and sapphire kettle is opened, by CO in equilibrium still2/CH4Mixed gas
It is injected into sapphire kettle, when pressure reaches 1.60MPa in sapphire kettle, closes valve；Wait for pressure stability in sapphire kettle,
Show that the adsorption process of modified activated carbon in sapphire kettle reaches balance, completes the CO at this time2/CH4CO in mixed gas2
Separation；
Pressure reading in equilibrium still and in sapphire kettle when recording adsorption equilibrium, and sapphire kettle inner equilibrium gas phase is carried out
Chromatography obtains after adsorption equilibrium CH in sapphire kettle inner equilibrium gas phase4Mole percent specific concentration and CO2Mole percent
Then specific concentration calculates the modified activated carbon to CO according to formula2/CH4CO in mixed gas2Adsorbance and described change
Property activated carbon is to CO2/CH4The separation factor of mixed gas.
Preferably, the sapphire kettle is cleaned and is dried with distilled water before containing the modified activated carbon.
Preferably, temperature control is carried out to sapphire kettle using air bath in the step 4.
Preferably, the hole appearance occupation rate of ethyl alcohol is calculated according to following formula in step 3 activated carbon：
In formula (1)~(3), RmImThe hole for representing 2-methylimidazole in modified activated carbon holds occupation rate, RglycolIt represents and is modified
The hole of ethylene glycol holds occupation rate, R in activated carbonethanolThe hole for representing ethyl alcohol in modified activated carbon holds occupation rate；
mwThe quality of modified activated carbon is represented, m represents the quality of dry activated carbon, mmImThe quality of 2-methylimidazole is represented,
mglycolRepresent the quality of ethylene glycol；
ρmImRepresent the density of 2-methylimidazole, ρglycolRepresent the density of ethylene glycol, ρethanolRepresent ethyl alcohol density；
V represents the t-plot micro pore volumes of modified activated carbon.
Preferably, calculation formula described in step 4 is as follows：
Step 1, the mixed gas molal quantity n that sapphire kettle initially enters is calculated0With after adsorption equilibrium in sapphire kettle put down
Weigh gas phase molal quantity nE：
Wherein,
In formula (4)~(6), P1For initial pressure in equilibrium still, P2For pressure in equilibrium still after adsorption equilibrium, PEFor absorption
Pressure in sapphire kettle after balance；V0For equilibrium still volume, VSIt is accumulated for sapphire autoclave body, V1For after adsorption equilibrium in sapphire kettle
Gaseous phase volume, T are system temperature；Z1、Z2And ZEEquilibrium still after initial gas phase compressibility factor, adsorption equilibrium respectively in equilibrium still
Gas phase compressibility factor in sapphire kettle after middle gas phase compressibility factor and adsorption equilibrium；
Step 2, it calculates and initially enters CH in sapphire kettle4Molal quantity n1And CO2Molal quantity n2：
n1=n0×z1 (7)
n2=n0×z2(8)；
Step 3, CH in sapphire kettle inner equilibrium gas phase is calculated after adsorption equilibrium4Molal quantityAnd CO2Molal quantity
Wherein, y1For CH in sapphire kettle inner equilibrium gas phase after adsorption equilibrium4Mole percent specific concentration, y2It is flat to adsorb
CO in sapphire kettle inner equilibrium gas phase after weighing apparatus2Mole percent specific concentration, and y1And y2It is by sapphire kettle inner equilibrium gas
Mutually carry out what chromatography obtained；
Step 4, CH in modified activated carbon absorption phase is calculated by mass balance4Molar fraction x1And CO2Molar fraction
x2：
Step 5, CH in calculated equilibrium gas phase4Rate of recovery R1：
Step 6, modified activated carbon is calculated to CO2Adsorbance M2：
M2=n0z2-nEy2(14)；
Step 7, modified activated carbon is calculated to CO2/CH4The separation factor β of mixed gas：
Preferably, initial gas phase compressibility factor Z in the equilibrium still1, gas phase is compressed in equilibrium still after the adsorption equilibrium
Factor Z2With gas phase compressibility factor Z in sapphire kettle after the adsorption equilibriumEIt is calculated by BWRS state equations, it is specific to count
It is as follows to calculate formula：
ZE=Z (T, P2,yi) (18)；
In formula (16)~(18), z1iFor the initial gas phase compressibility factor of each component in equilibrium still, z2iTo be balanced after adsorption equilibrium
Each component gas phase compressibility factor, y in kettleiMolar percentage for each component in sapphire kettle inner equilibrium gas phase after adsorption equilibrium is dense
Degree.
Compared with prior art, the beneficial effects of the present invention are：
The present invention in activated carbon surface by loading 2-methylimidazole, ethyl alcohol and ethylene glycol, on the one hand, 2-methylimidazole point
The N atoms of son can form hydrogen bond with the ethyl alcohol of activated carbon surface, the hydroxyl of glycol molecule, and film is formed in activated carbon surface,
Hinder CH4Molecular Adsorption is to activated carbon surface；On the other hand, CO2Molecule can react that form one kind include N- with 2-methylimidazole
The carbamate of C keys then improves activated carbon to CO2Adsorptive selectivity.Therefore, the present invention by 2-methylimidazole, ethyl alcohol,
Ethylene glycol is supported on activated carbon surface, substantially increases activated carbon to CO2/CH4The separating effect of gaseous mixture.
Specific implementation mode
In order to enable those skilled in the art to more fully understand, technical scheme of the present invention is practiced, with reference to specific
The invention will be further described for embodiment, but illustrated embodiment is not as a limitation of the invention.
Experimental method and detection method described in following embodiment and comparative examples are unless otherwise specified conventional method；
The reagent and material can be commercially available on the market unless otherwise specified.
It should be noted that containing CO used in embodiment and comparative example2/CH4Mixed gas use human configuration mould
It is quasi-, and the CH containing 78.02mol% in mixed gas4With the CO of 21.98mol%2, activated carbon used is equal in embodiment and comparative example
For Sigma activated carbons, wherein the performance of Sigma activated carbons is shown in Table 1.
The structure feature of table 1Sigma activated carbons
Explanation is needed further exist for, equipment therefor is this field conventional equipment in embodiment and comparative example, with chemical industry
Volume 67 of journal 2016, the 10th interim paper delivered《Two in 2-methylimidazole/glycol system room temperature removing natural gas
Carbonoxide》Used in apparatus structure it is identical, and in the embodiment of the present invention and comparative example equilibrium still used volume V0For
110cm3, maximum working pressure 50MPa, using stainless steel Cr17Ni14Mo2Material is made, and there are one pressure for installation on equilibrium still
Sensor, pressure data can be acquired by computer；
Sapphire kettle is manufactured by Canadian DBRobinson companies, volume VSFor 34.14cm3, maximum working pressure is
20MPa, operating temperature range are -90~150 DEG C.A pressure sensor is mounted with above sapphire kettle, pressure data can
It is acquired by computer.Pressure change controls (Jiangsu Hai'an oil instrument by the high pressure hand-operated metering pump of JP-III types in sapphire kettle
Factory produces).
The present invention carries out temperature control using constant temperature air bath to sapphire kettle, and constant temperature air bath is the height being balanced with heat
Control, and the temperature uniformity of air bath is adjusted by Intelligent Digital temperature controller in warm experimental box, internal temperature
For ± 0.3K, precision is ± 0.1K；
The Pt100 type precision platinum resistance that sapphire temperature in the kettle is mounted on by one in sapphire kettle bottom head covers is surveyed
It is fixed.The pressure value of experimental system is 0.1 grade by two precision in the present invention, and range is the HEISE precision pressures of 0~10MPa
Sensor measures in real time, and the temperature, pressure automatic collection software write by the Kunlun configuration software MCGS is acquired.At this
In experiment, the error of pressure measuring value is ± 0.01MPa.
Embodiment 1
A kind of CO2/CH4CO in mixed gas2Separation method, include the following steps：
Step 1, under vacuum, by quality mwIt is dried at 120 DEG C for 24 hours, after dry for the activated carbon of 6.30g
It is cooled to room temperature, obtains the dry activated carbon that quality m is 3.30g；
Step 2, by quality mmIm2-methylimidazole, quality m for 1.01gglycolIt is for the ethylene glycol and quality of 1.64g
The ethyl alcohol of 10g is uniformly mixed, and obtains mixed solution；
The 3.30g dry activated carbons obtained in step 1 are uniformly mixed with 12.65g mixed solutions, obtain solid-liquid mixing
Object；
Step 3, solidliquid mixture in step 2 is stood one week under vacuum, it is then dry at 80 DEG C, and dry
It is dry during monitoring activated carbon in ethyl alcohol hole hold occupation rate, when monitor ethyl alcohol in activated carbon hole hold occupation rate reach
When 10.20%, that is, terminate drying, obtains modified activated carbon；
Wherein, the hole appearance occupation rate of ethyl alcohol is calculated according to following formula in activated carbon in monitoring process：
Wherein, mwFor 6.30g, m 3.30g, mmImFor 1.01g, mglycolFor 1.64g；ρmImFor 1.030g/mL, ρglycoll
For 1.115g/mL, ρethanolFor 0.789g/mL；V is 1.49cm3/ g, is obtained by calculation RmImFor 20%, RglycollFor
30.00%, RethanolIt is 10.20%；
Step 4, modified activated carbon in step 3 is placed in sapphire kettle, sapphire kettle with valvular pipeline by connecting
It is connected with equilibrium still, sapphire kettle and the valve on equilibrium still connecting pipeline is closed, equilibrium still and its institute's connecting leg road is vacuumized, waited for
After air drains in equilibrium still and its institute's connecting leg road, by CO2/CH4Mixed gas is squeezed into equilibrium still
3.70MPa；
Temperature control is carried out to sapphire kettle, when sapphire kettle temperature degree stablizes the pressure stability in 10 DEG C and equilibrium still, record
The pressure reading P of equilibrium still1For 3.62MPa；Sapphire kettle and its institute's connecting leg road are vacuumized simultaneously, wait for sapphire kettle and its institute
After air drains in connecting leg road, the valve on connecting pipeline between equilibrium still and sapphire kettle is opened, by CO in equilibrium still2/CH4
Mixed gas is injected into sapphire kettle, when pressure reaches 1.60MPa in sapphire kettle, closes valve；Wait for sapphire kettle and
Pressure is stablized in equilibrium still, shows that the adsorption process of modified activated carbon in sapphire kettle reaches balance, completes CO at this time2/
CH4CO in mixed gas2Separation；
Pressure reading P in equilibrium still when recording adsorption equilibrium2For 3.23MPa, pressure reading P in sapphire kettleEFor
1.43MPa, and chromatography is carried out to sapphire kettle inner equilibrium gas phase, obtain CH in modified activated carbon absorption phase4Moles hundred
Divide CO in specific concentration and modified activated carbon absorption phase2Mole percent specific concentration, then according to formula calculate modified activated carbon pair
CO2/CH4CO in mixed gas2Adsorbance, and to CO2/CH4The separation factor of mixed gas, specific calculating process are as follows：
Step 1, the mixed gas molal quantity n that sapphire kettle initially enters is calculated0With gas in sapphire kettle after adsorption equilibrium
Phase molal quantity nE：
Wherein,
In formula (4)~(6), P1For 3.62MPa, P2For 3.23MPa, PEFor 1.43MPa, V0For 110cm3, VSFor
34.14cm3, R is 8.314J/ (molK), T 283K, Z1、Z2、ZECalculated respectively 0.90 by BWRS state equations,
0.91、0.96；N is calculated by formula (4)~(6)0For 22.08mmol, nEFor 18.36mmol；
Step 2, it calculates and initially enters CH in sapphire kettle4Molal quantity n1And CO2Molal quantity n2：
n1=n0×z1 (7)
n2=n0×z2(8)；
N is calculated by formula (7)~(8)1For 17.23mmol, n2For 4.85mmol；
Step 3, CH in sapphire kettle inner equilibrium gas phase is calculated after adsorption equilibrium4Molal quantityAnd CO2Molal quantity
By carrying out chromatography to sapphire kettle inner equilibrium gas phase, y is obtained1For 88.41%, y2It is 11.59%, passes through
Formula (9)~(10) are calculatedFor 16.23mmol,For 2.13mmol；
Step 4, CH in modified activated carbon absorption phase is calculated by mass balance4Molar fraction x1And CO2Molar fraction
x2：
X is calculated by formula (11)~(12)1For 26.78%, x2It is 73.22%；
Step 5, CH in calculated equilibrium gas phase4Rate of recovery R1For：
R is calculated by formula (13)1It is 94.21%；
Step 6, modified activated carbon is calculated to CO2Adsorbance M2：
M2=n0z2-nEy2(14)；
M is calculated by formula (14)2For 0.83mmol/g；
Step 7, modified activated carbon is calculated to CO2/CH4The separation factor β of mixed gas：
It is 20.86 by the β that is calculated of formula (15).
Effect in order to further illustrate the present invention, the present invention is also provided with comparative example, specific as follows：
Comparative example 1
Non-modified 3.30g activated carbons are placed in sapphire kettle, are closed on sapphire kettle and equilibrium still connecting pipeline
Valve, equilibrium still and its institute's connecting leg road are vacuumized, after air drains in ready to balance kettle and its institute's connecting leg road, by CO2/CH4It is mixed
Close gas squeeze into equilibrium still to preset pressure be 3.70MPa；
Temperature control is carried out to sapphire kettle, when sapphire kettle temperature degree stablizes the pressure stability in 10 DEG C and equilibrium still, record
The pressure reading P of equilibrium still1For 3.66MPa；Sapphire kettle and its institute's connecting leg road are vacuumized simultaneously, wait for sapphire kettle and its institute
After air drains in connecting leg road, the valve on connecting pipeline between equilibrium still and sapphire kettle is opened, by CO in equilibrium still2/CH4
Mixed gas is injected into sapphire kettle, when pressure reaches 1.60MPa in sapphire kettle, closes valve；
Wait for that pressure is stablized in sapphire kettle and equilibrium still, shows that the adsorption process of activated carbon in sapphire kettle reaches flat
Weighing apparatus completes CO at this time2/CH4CO in mixed gas2Separation；
P in equilibrium still when record balance2For 3.29MPa, pressure reading P in sapphire kettleEFor 1.54MPa, and to sapphire
Kettle inner equilibrium gas phase carries out chromatography, obtains after adsorption equilibrium in sapphire kettle CH in gas phase4Molar concentration y1For
83.92%, CO in gas phase in sapphire kettle after adsorption equilibrium2Molar concentration y2It is 16.08%, is then calculated and lived according to formula
Property charcoal is to CO2/CH4CO in mixed gas2Adsorbance, and to CO2/CH4The separation factor of mixed gas.
Calculating process is the same as embodiment 1, wherein P1For 3.66MPa, P2For 3.29MPa, PEFor 1.54MPa, V0For 110cm3,
VSFor 34.14cm3, R is 8.314J/ (molK), T 283K, Z1、Z2、ZEIt is calculated respectively by BWRS state equations
089、0.90、0.96；y1For 83.92%, y2It is 16.08%, it is as follows that result is obtained by calculation：
n0=26.91mmol, nE=21.93mmol, n1For 21.00mmol, n2For 5.92mmol, n1 EFor 18.40mmol,For 3.53mmol, x1=52.06%, x2=47.94%；
Balance CH in gas phase4Rate of recovery R1It is 89.82%, activated carbon is to CO2Adsorbance M2It is living for 0.72mmol/g
Property charcoal is to CO2/CH4The separation factor β of mixed gas is 5.30.
The data obtained from embodiment 1 and comparative example 1 can be seen that in the same adsorption test of use to CO2/CH4Mixing
CO in gas2When being detached, CH in balance gas phase is finally calculated in the activated carbon not being modified4Rate of recovery R1For
89.82%, activated carbon is to CO2Adsorbance M2For 0.72mmol/g, activated carbon is to CO2/CH4The separation factor β of mixed gas is
5.30；And CH in balance gas phase is finally calculated in the activated carbon after 2-methylimidazole, ethylene glycol and ethanol modifier4Recycling
Rate R1It is 94.21%, activated carbon is to CO2Adsorbance M2For 0.83mmol/g, activated carbon is to CO2/CH4The separation of mixed gas because
Sub- β is 20.86, and properties are superior to unmodified activated carbon, is illustrated with 2-methylimidazole, ethylene glycol, ethyl alcohol to activity
The method that charcoal is modified is to detaching CO2/CH4CO in gaseous mixture2And CO absorption2It is significantly improved.
Reason is analyzed, is activated carbon surface load 2-methylimidazole, ethyl alcohol and ethylene glycol because modified, on the one hand,
The N atoms of 2-methylimidazole molecule can form hydrogen bond with the ethyl alcohol of activated carbon surface, the hydroxyl of glycol molecule, in activated carbon
Surface forms film, hinders CH4Molecular Adsorption is to activated carbon surface；On the other hand, CO2Molecule can react to be formed with 2-methylimidazole
A kind of includes the carbamate of N-C keys, then improves activated carbon to CO2Adsorptive selectivity.Therefore, the present invention is by 2- first
Base imidazoles, ethyl alcohol, ethylene glycol are supported on activated carbon surface, substantially increase activated carbon to CO2/CH4The separating effect of gaseous mixture.
It should be noted that involved in claims of the present invention when numberical range, it is thus understood that each numberical range
Any one numerical value can be selected between two endpoints and two endpoints, since the step method of use is same as Example 1,
It repeats in order to prevent, the present invention describes preferred embodiment, is created once a person skilled in the art knows basic
Property concept, then additional changes and modifications may be made to these embodiments.So it includes excellent that the following claims are intended to be interpreted as
It selects embodiment and falls into all change and modification of the scope of the invention.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art
God and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent technologies
Within be also intended to include these modifications and variations.
Claims (6)
1. a kind of CO2/CH4CO in mixed gas2Separation method, which is characterized in that include the following steps：
Step 1, under vacuum, by activated carbon, drying for 24 hours, is cooled to room temperature after dry, obtains drying at 120 DEG C
Activated carbon；
Step 2, by 2-methylimidazole, ethylene glycol, ethyl alcohol according to 1.01：1.64：10 mass ratio is uniformly mixed, and obtains mixing molten
Liquid；
By the dry activated carbon obtained in step 1 and the mixed solution according to 3.3：12.65 mass ratio mixing, obtains solid-liquid
Mixture；
Step 3, solidliquid mixture in step 2 is stood one week under vacuum, it is then dry at 80 DEG C, and dried
In journey monitor activated carbon in ethyl alcohol hole hold occupation rate, when monitor ethyl alcohol in activated carbon hole hold occupation rate reach 10% or more
When, that is, terminate drying, obtains modified activated carbon；
Step 4, modified activated carbon in step 3 is placed in sapphire kettle, sapphire kettle with valvular pipeline connection by having
Equilibrium still is closed sapphire kettle and the valve on equilibrium still connecting pipeline, is vacuumized to equilibrium still and its institute's connecting leg road, ready to balance
After air drains in kettle and its institute's connecting leg road, by CO2/CH4Mixed gas squeeze into equilibrium still to preset pressure be 3.70MPa；
Temperature control is carried out to sapphire kettle, when sapphire temperature in the kettle stablizes the pressure stability in 10 DEG C and equilibrium still, record is flat
The pressure reading of weighing apparatus kettle；Sapphire kettle and its institute's connecting leg road are vacuumized simultaneously, wait for air in sapphire kettle and its institute's connecting leg road
After draining, the valve on connecting pipeline between equilibrium still and sapphire kettle is opened, by CO in equilibrium still2/CH4Mixed gas is injected
Into sapphire kettle, when pressure reaches 1.60MPa in sapphire kettle, valve is closed；It waits for pressure stability in sapphire kettle, shows
The adsorption process of modified activated carbon reaches balance in sapphire kettle, completes the CO at this time2/CH4CO in mixed gas2Point
From；
Pressure reading in equilibrium still and in sapphire kettle when recording adsorption equilibrium, and chromatography is carried out to sapphire kettle inner equilibrium gas phase
Analysis obtains after adsorption equilibrium CH in sapphire kettle inner equilibrium gas phase4Mole percent specific concentration and CO2Molar percentage it is dense
Then degree calculates the modified activated carbon to CO according to formula2/CH4CO in mixed gas2Adsorbance and described modified living
Property charcoal is to CO2/CH4The separation factor of mixed gas.
2. CO according to claim 12/CH4CO in mixed gas2Separation method, which is characterized in that the sapphire
Kettle is cleaned and is dried with distilled water before containing the modified activated carbon.
3. CO according to claim 12/CH4CO in mixed gas2Separation method, which is characterized in that in the step 4
Temperature control is carried out to sapphire kettle using air bath.
4. CO according to claim 12/CH4CO in mixed gas2Separation method, which is characterized in that the step 3 is lived
Property charcoal in ethyl alcohol hole hold occupation rate calculated according to following formula：
In formula (1)~(3), RmImThe hole for representing 2-methylimidazole in modified activated carbon holds occupation rate, RglycolRepresent modified active
The hole of ethylene glycol holds occupation rate, R in charcoalethanolThe hole for representing ethyl alcohol in modified activated carbon holds occupation rate；
mwThe quality of modified activated carbon is represented, m represents the quality of dry activated carbon, mmImRepresent the quality of 2-methylimidazole, mglycol
Represent the quality of ethylene glycol；
ρmImRepresent the density of 2-methylimidazole, ρglycolRepresent the density of ethylene glycol, ρethanolRepresent ethyl alcohol density；
V represents the t-plot micro pore volumes of modified activated carbon.
5. CO according to claim 12/CH4CO in mixed gas2Separation method, which is characterized in that described in step 4
Calculation formula is as follows：
Step 1, the mixed gas molal quantity n that sapphire kettle initially enters is calculated0With sapphire kettle inner equilibrium gas phase after adsorption equilibrium
Molal quantity nE：
Wherein,
In formula (4)~(6), P1For initial pressure in equilibrium still, P2For pressure in equilibrium still after adsorption equilibrium, PEFor adsorption equilibrium
Pressure in sapphire kettle afterwards；V0For equilibrium still volume, VSIt is accumulated for sapphire autoclave body, V1For gas phase in sapphire kettle after adsorption equilibrium
Volume, T are system temperature；Z1、Z2And ZEGas in equilibrium still after initial gas phase compressibility factor, adsorption equilibrium respectively in equilibrium still
Gas phase compressibility factor in sapphire kettle after phase compressibility factor and adsorption equilibrium；
Step 2, it calculates and initially enters CH in sapphire kettle4Molal quantity n1And CO2Molal quantity n2：
n1=n0×z1 (7)
n2=n0×z2(8)；
Step 3, CH in sapphire kettle inner equilibrium gas phase is calculated after adsorption equilibrium4Molal quantityAnd CO2Molal quantity
Wherein, y1For CH in sapphire kettle inner equilibrium gas phase after adsorption equilibrium4Mole percent specific concentration, y2After adsorption equilibrium
CO in sapphire kettle inner equilibrium gas phase2Mole percent specific concentration, and y1And y2Be by sapphire kettle inner equilibrium gas phase into
Row chromatography obtains；
Step 4, CH in modified activated carbon absorption phase is calculated by mass balance4Molar fraction x1And CO2Molar fraction x2：
Step 5, CH in calculated equilibrium gas phase4Rate of recovery R1：
Step 6, modified activated carbon is calculated to CO2Adsorbance M2：
M2=n0z2-nEy2(14)；
Step 7, modified activated carbon is calculated to CO2/CH4The separation factor β of mixed gas：
6. CO according to claim 52/CH4CO in mixed gas2Separation method, which is characterized in that the equilibrium still
In initial gas phase compressibility factor Z1, gas phase compressibility factor Z in equilibrium still after the adsorption equilibrium2With blue treasured after the adsorption equilibrium
Gas phase compressibility factor Z in stone kettleEIt is calculated by BWRS state equations, specific formula for calculation is as follows：
Z1=Z (T, P1,z1i) (16)
Z2=Z (T, P2,z2i) (17)
ZE=Z (T, P2,yi) (18)；
In formula (16)~(18), z1iFor the initial gas phase compressibility factor of each component in equilibrium still, z2iFor in equilibrium still after adsorption equilibrium
Each component gas phase compressibility factor, yiFor the Mole percent specific concentration of each component in sapphire kettle inner equilibrium gas phase after adsorption equilibrium.
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| CN112044233A (en) * | 2019-06-05 | 2020-12-08 | 中冶长天国际工程有限责任公司 | Method and system for calculating discharge amount of roller feeder in activated carbon method flue gas purification system |
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