CN106969999A - A kind of true High Pressure Absorption kinetic test device and method of adsorbent - Google Patents
A kind of true High Pressure Absorption kinetic test device and method of adsorbent Download PDFInfo
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Abstract
Of the invention to provide a kind of true High Pressure Absorption kinetic test device and method of adsorbent, methods described is the volumetric method based on static bed test system after improvement, including volumetric calibration, hot-zone cold-zone are demarcated, hunted leak, four steps of test.This method makes pressure gauge in traditional static bed test system into high sensitivity pressure sensor, pass through the true High Pressure Absorption kinetic curve of pressure versus time curve inverse adsorbent in adsorption tube, it is to avoid influence of the feed rate to test result in conventional adsorbent kinetic test method；The concept and measuring method of hot-zone cold-zone are proposed, is reduced due to the calculation error that pipeline dead volume and adsorption tube temperature unevenness are caused.This method also proposed by controlling to add the method for sample quality in adsorption tube so that the pressure drop macroscopic view of measurement process is small microcosmic big, not only can guarantee that the accuracy of result of calculation but also can be approximately considered adsorption process pressure and is basically unchanged.
Description
Technical field
The invention belongs to adsorbent characterization technique field, and in particular to a kind of true High Pressure Absorption kinetic test of adsorbent
Device and method.
Background technology
Adsorbent be it is a kind of can effectively absorb the solid matter of some compositions in gas, be widely used in needing carrying out
Gas separate and purification field, including the industry such as oil, chemical industry, metallurgy, generating.Adsorbent can divide according to use condition difference
For normal temperature physical absorbent (activated carbon, zeolite, silica gel, aluminum oxide), normal temperature chemosorbent (solid amine, sodium carbonate), middle temperature
Adsorbent (the double salt of hydrotalcite, magnesium-based) and high-temperature adsorbing agent (lithium metasilicate, lithium zirconate, calcium oxide) etc..Evaluate performance of the adsorbent
Index mainly includes adsorbance and adsorption dynamics adsorption kinetics.It is general using thermogravimetric analyzer (Thermal Gravimetric at present
Analyzer, TGA), obtain the absorption power of adsorbent by measuring gain in weight of the adsorbent in adsorbate atmosphere
Learn.But conventional TGA can only measure below 1atm absorption property；According to high pressure TGA, then inhaled test initial stage in absorption
Attached gas needs the high-pressure inert gas in replacement test chamber, therefore obtained adsorption curve is limited by feed rate.Separately
A kind of method for characterizing adsorbent High Pressure Absorption performance is to test breakthrough curve using fixed bed.The method is to being filled with adsorbent
Adsorbate is passed through in fixed bed reactors, the breakthrough curve and blank curve that adsorbate is exported by contrasting are inhaled
Attached dose of High Pressure Absorption amount.The breakthrough curve shape obtained in this way is substantially inhaled by adsorbent under different partial pressures
The influence of attached characteristic, it is additionally related to the mass transfer characteristic of fixed bed, therefore more difficult therefrom extraction adsorbent kinetic parameter, one
As be used for Adsorption Model checking.In some practical application in industry, adsorbent needs to work at elevated pressures.For example for
Collecting carbonic anhydride and coal chemical industry regulation C/Hratio technique before power plant combustion, the synthesis gas stagnation pressure of required processing is 3-5MPa, its
Middle CO2Partial pressure is about 1-1.5MPa.Normal pressure Adsorption Model based on TGA experimental datas can not be applied to this kind of operating mode.In order to obtain
The fitting parameter needed for adsorbent High Pressure Absorption model must be built, it is necessary to be carried out to the true High Pressure Absorption dynamics of adsorbent real
Test is tried.Absorption isotherm of the volumetric method based on common static bed available for measurement adsorbent, but document and patent at present
In do not have using volumetric method measure adsorbent hyperbolic kinetics relevant report.Volumetric method is unrestricted due to feed rate, because
This is possible to the true High Pressure Absorption dynamics for obtaining adsorbent.The present invention is improved to traditional static bed, and is based on changing
Test system after entering proposes a kind of dynamic (dynamical) method of testing of true High Pressure Absorption of adsorbent.
The content of the invention
The present invention carries out technological improvement on the basis of traditional static bed test device, and proposes one kind based on volumetric method
The dynamic (dynamical) test device of the true High Pressure Absorption of adsorbent and method.
A kind of true High Pressure Absorption kinetic test device of adsorbent, including copper coasting body heating furnace, adsorption tube V2, absorption
Pipe V1, vavuum pump, tee ball valve, pressure-reducing valve, computer, needle-valve 1, pressure sensor, needle-valve 2；The pressure-reducing valve left end connects steel
Bottle gas, right-hand member connects tee ball valve；Two-way is separated above and below the tee ball valve, upper road connects needle-valve 1, pressure sensor and needle-valve successively
2, lower road connects vavuum pump；Measurement signal is transmitted to computer and preserved by the pressure sensor；The adsorption tube V1With adsorption tube V2
Needle-valve 1 and the downstream of needle-valve 2 are respectively connected to, and is positioned in copper coasting body heating furnace.
Further, the pressure sensor is to spread silicon type, deposition tube resistance type or capacitance-type, accuracy class≤
0.5%FS, corresponding time≤1s, output signal is 4-20mA.The sensor of multiple different ranges is set in the range of 0-10MPa
To improve the measurement accuracy in the range of each pressure measurement.
A kind of true High Pressure Absorption kinetic test method of adsorbent, methods described uses said apparatus, and including as follows
Step：Step 1 volumetric calibration, step 2 hot-zone cold-zone demarcation, step 3 is hunted leak and step 4 is tested.
Wherein, step 1 volumetric calibration (steel ball method), comprises the following steps：
(1) step, holding meanss are in room temperature T0, and environment temperature remains stable during calibration；
(2) step, switching three-way ball valve causes needle-valve 1 to be connected with vavuum pump, needle-valve 1 and needle-valve 2 is opened, by adsorption tube
V1With adsorption tube V2It is evacuated to vacuum；
(3) step, closes needle-valve 2, switching three-way ball valve causes pressure-reducing valve to be connected with needle-valve 1, to adsorption tube V1In be filled with
Pressure is p11Helium；
(4) step, closes needle-valve 1 and opens needle-valve 2, by adsorption tube V1With adsorption tube V2Connection, record pressure is p12；
(5) step, changes p11Value, repeat step two to step 4 1-10 time, the corresponding p of record12；
(6) step, inquiry helium is in the density p (p corresponding to each pressure spot11, T0) and ρ (p12, T0), and to its carry out
Linear regression, is obtainedWherein k1 is fit slope；
(7) step, to adsorption tube V2Middle addition cumulative volume is V02Standard steel ball, repeat step (two) to step (6),
Gained pressure is designated as p21And p22, obtainWherein k2 is fit slope；
(8) step, changes and adds adsorption tube V2(2) volume of steel ball in, repeat step (seven) 1-10 times, obtains ki, i=
1,2,3 ..., to gained kiAnd V0iLinear regression is carried out, is obtainedWherein V01=0, then adsorption tube V1(3) and
Adsorption tube V2(2) volume is respectivelyV2=(b-1) V1, wherein a and ki are fit slope, and b is fitting intercept；
Step 2. hot-zone cold-zone is demarcated, and it comprises the following steps：
(1) step, to adsorption tube V2In insert the standard steel ball close with testing sample volume, total volume meter is V0；
(2) step, in room temperature T0It is lower to adsorption tube V1With adsorption tube V2Middle charged pressure is p1Helium, close needle-valve 1
With needle-valve 2；
(3) step, Heated Copper coasting body heating furnace to test temperature T2And remain stable, record now pressure data p2；
(4) step, opens needle-valve 2, by adsorption tube V1With adsorption tube V2Connection, record pressure is p3；
(5) step, switching three-way ball valve causes needle-valve 1 to be connected with vavuum pump, needle-valve 1 is opened, by adsorption tube V1And absorption
Pipe V2It is evacuated to vacuum；
(6) step, closes needle-valve 2, switching three-way ball valve causes pressure-reducing valve to be connected with needle-valve 1, to adsorption tube V1In be filled with
Pressure is p4Test gas；
(7) step, closes needle-valve 1 and opens needle-valve 2, by adsorption tube V1With adsorption tube V2Connection, record pressure is p5；
(8) step, changes p4Value, repeats (six) to step (7) 1-10 time, the corresponding p of record5；
(9) step, it is assumed that cold-zone temperature isCalculating obtains adsorption tube V1With adsorption tube V1+ adsorption tube V2Cold-zone body
Product accounts for the ratio between cumulative volumeWithRespectively
(10) step, test gas density is designated as ρ ', calculates in different pressures p5The lower obtained steel ball cumulative volume tested isWherein Make
Go outWith p5Change curve；
(11) step, changing cold-zone temperature isWherein i=1,2,3 ..., repeat step (nine) to step (10),
Suitable cold-zone temperature is found using dichotomySo that calculating what is obtainedWith actual value V0Close and basic and p5Value without
Close, then obtain cold-zone temperature
Step 3. is hunted leak, and it comprises the following steps：
(1) step, Heated Copper coasting body heating furnace to test temperature T2And remain stable, to adsorption tube V1With adsorption tube V2
Middle charged pressure is p1Test gas；
(2) step, closes needle-valve 1 and opens needle-valve 2, test 1-72 hour, p in the unit of account time1Variable quantity
(absolute value), is designated as slip δ.
Step 4. is tested, and it comprises the following steps：
(1) step, to adsorption tube V2Middle addition quality is msTesting sample, holding meanss be in room temperature T0；
(2) step, switching three-way ball valve causes needle-valve 1 to be connected with vavuum pump, needle-valve 1 and needle-valve 2 is opened, by adsorption tube
V1With adsorption tube V2It is evacuated to vacuum；
(3) step, closes needle-valve 2, switching three-way ball valve causes pressure-reducing valve to be connected with needle-valve 1, to adsorption tube V1In be filled with
Pressure is p1Helium；
(4) step, closes needle-valve 1 and opens needle-valve 2, by adsorption tube V1With adsorption tube V2Connection, record pressure is p2；
(5) step, calculating sample volume is
(6) step, by adsorption tube V1With adsorption tube V2It is evacuated to vacuum, Heated Copper coasting body heating furnace to test temperature T2And
Remain stable；
(7) step, closes needle-valve 2, switching three-way ball valve causes pressure-reducing valve to be connected with needle-valve 1, to adsorption tube V1In be filled with
Pressure is p3Test gas；
(8) step, closes needle-valve 1 and opens needle-valve 2, by adsorption tube V1With adsorption tube V2Connection, record pressure is with the time
Change p4(t)；
(9) step, it is assumed that pressure p4In t=t∞When tend towards stability, then can obtain adsorbent temperature be T2, pressure is p4
(t∞) when the true adsorption curve of HTHP beIts
In Mg
To test the molal weight of gas.
(10) step, changes p3Size, it is T that repeat step (seven) to step (9), which can be obtained in temperature,2When different pressures under
True High Pressure Absorption curve.
Wherein, in the step 1 (seven) step the single -20mm of diameter 1 of standard steel ball, volumetric errors≤0.1%.
Wherein, (one) step testing sample includes activated carbon, zeolite, silica gel, aluminum oxide, solid amine, carbon in the step 4
Sour sodium, hydrotalcite, magnesium-based double salt, lithium metasilicate, lithium zirconate, calcium oxide etc..
Wherein, the addition quality m of the testing samplesIt should ensure that the pressure drop p in test process4(t0)-p4(t∞) do not surpass
Cross p4(t0) 20%, but higher than pressure sensor resolution.
Wherein, the step 2 is to the test temperature T described in step 42For 200-1000K, (nine) step in step 4
Test pressure p4(t∞) it is 0-10MPa.
Wherein, the test gas of (seven) step includes carbon monoxide, carbon dioxide, oxygen, nitrogen, hydrogen in the step 4
Gas, hydrogen sulfide, sulfur dioxide, cos, alkane, formaldehyde, acetaldehyde or nitrogen oxides etc..
Beneficial effects of the present invention are：
1. making pressure gauge in traditional static bed test system into high sensitivity pressure sensor, pass through pressure in adsorption tube
The true High Pressure Absorption kinetic curve of versus time curve inverse adsorbent, it is to avoid conventional adsorbent kinetic test
Influence of the feed rate to test result in method.
2. proposing the concept and measuring method of hot-zone cold-zone, adsorption tube and the pipeline connected are divided into cold-zone and hot-zone,
The temperature and accounting of cold-zone are demarcated according to experimental data.The division of cold-zone and hot-zone reduce due to pipeline dead volume and
The calculation error that adsorption tube temperature unevenness is caused；
3. proposing the methods of measurement and calculation of adsorbent hyperbolic kinetics curve, absorbing under test gas by adsorbent causes
Adsorb overpressure and decline inverse adsorption curve, it is to avoid due to measuring caused by the limitation of feed rate in other measuring methods
Error.Make it that pressure drop macroscopic view is small microcosmic big in measurement process by the quality for the adsorbent for controlling to add adsorption tube, Ji Nengbao
Card result of calculation has enough accuracy, and adsorption process test pressure can be approximately considered again and is basically unchanged.The method of testing can be wide
The general performance of the adsorbent for being applied to include in the industries such as oil, chemical industry, metallurgy, generating is characterized, and is adsorbent High Pressure Absorption model
Foundation provide fitting and checking experimental data.
Brief description of the drawings
Fig. 1 is used for the static bed apparatus structural representation of true High Pressure Absorption kinetic test for the present invention.
Fig. 2 is hot-zone and cold-zone schematic diagram in the demarcating steps of hot-zone cold-zone of the present invention.
Fig. 3 is that steel ball method demarcates linear regression result.
Fig. 4 is test system leak detection result.
Fig. 5 is Taixi anthracite column-shaped active carbon high pressure CO2Adsorption curve (test temperature：15℃).
Fig. 6 is hot-zone cold-zone demarcating steps heating curve.
Fig. 7 is K-MG30 high pressure COs2Adsorption curve (test temperature：400℃).
Table 1 is using steel ball body of laws product calibration result.
Table 2 is hot-zone cold-zone calibration result.
Label in figure：1- copper coasting body heating furnaces；2- adsorption tubes V2；3- adsorption tubes V1；4- vavuum pumps；5- tee ball valves；6-
Pressure-reducing valve；7- computers；8- needle-valves 1；9- pressure sensors；10- needle-valves 2.
Embodiment
The invention provides a kind of dynamic (dynamical) test device of the true High Pressure Absorption of adsorbent and method, below in conjunction with the accompanying drawings
The present invention will be further described with embodiment.
A kind of true high-temperature high-pressure adsorption kinetic test device of adsorbent, described device includes copper coasting body heating furnace 1,
Adsorption tube V22, adsorption tube V13, vavuum pump 4, tee ball valve 5, pressure-reducing valve 6, computer 7, needle-valve 18, pressure sensor 9, needle-valve
2 10；The left end of pressure-reducing valve 6 connects steel cylinder gas, and right-hand member connects tee ball valve 5；The tee ball valve separates two-way about 5, upper road according to
Secondary to connect needle-valve 18, pressure sensor 9 and needle-valve 2 10, lower road connects vavuum pump 4；The pressure sensor 9 transmits measurement signal
Preserved to computer 7；The adsorption tube V13 and adsorption tube V22 are respectively connected to needle-valve 1 and the downstream of needle-valve 2, and are positioned over copper inertia
In body heating furnace 1.The pressure sensor 9 is to spread silicon type, deposition tube resistance type or capacitance-type, accuracy class≤
0.5%FS, corresponding time≤1s, output signal is 4-20mA.The pressure of multiple different ranges is set to pass in the range of 0-10MPa
Sensor 9.
Using said apparatus carry out the dynamic (dynamical) method of testing of the true High Pressure Absorption of adsorbent, the method for testing be based on
The volumetric method of static bed test device after improvement, comprises the following steps：
Step 1. volumetric calibration；
Step 2. hot-zone cold-zone is demarcated
Step 3. is hunted leak
Step 4. is tested.
Step 1 volumetric calibration (steel ball method) step is as follows：
(1) step, holding meanss are in room temperature T0, and environment temperature remains stable during calibration；
(2) step, switching three-way ball valve 5 causes needle-valve 18 to be connected with vavuum pump 4, opens needle-valve 1 and needle-valve 2 10, will
Adsorption tube V13 and adsorption tube V22 are evacuated to vacuum；
(3) step, closes needle-valve 2, switching three-way ball valve 5 causes pressure-reducing valve 6 to be connected with needle-valve 1, to adsorption tube V1In 3
Charged pressure is p11Helium；
(4) step, closes needle-valve 1 and opens needle-valve 2, by adsorption tube V13 and adsorption tube V22 connections, recording pressure is
p12；
(5) step, changes p11Value, repeat step (two) to step (4) 1-10 time, the p corresponding to record12；
(6) step, inquiry helium is in the density p (p corresponding to each pressure spot11, T0) and ρ (p12, T0), and to its carry out
Linear regression, is obtainedWherein k1 is fit slope；
(7) step, to adsorption tube V2Middle addition cumulative volume is V02Standard steel ball, repeat step (two) to step (6),
Gained pressure is designated as p21And p22, obtainWherein k2 is fit slope；
(8) step, changes and adds adsorption tube V2(2) volume of steel ball in, repeat step (seven) 1-10 times, obtains ki, i=
1,2,3 ..., to gained kiAnd V0iLinear regression is carried out, is obtainedWherein V01=0, then adsorption tube V1(3) and
Adsorption tube V2(2) volume is respectivelyV2=(b-1) V1, wherein a and ki are fit slope, and b is fitting intercept；
Step 2 hot-zone cold-zone demarcating steps are as follows：
(1) step, to adsorption tube V2The standard steel ball close with testing sample volume is inserted in 2, total volume meter is V0；
(2) step, in room temperature T0It is lower to adsorption tube V13 and adsorption tube V2Charged pressure is p in 21Helium, close needle-valve
1 and needle-valve 2；
(3) step, Heated Copper coasting body heating furnace to test temperature T2And remain stable, record now pressure data p2；
(4) step, opens needle-valve 2, by adsorption tube V13 and adsorption tube V22 connections, record pressure is p3；
(5) step, switching three-way ball valve 5 causes needle-valve 1 to be connected with vavuum pump 4, needle-valve 1 is opened, by adsorption tube V13 Hes
Adsorption tube V22 are evacuated to vacuum；
(6) step, closes needle-valve 2, switching three-way ball valve 5 causes pressure-reducing valve 6 to be connected with needle-valve 1, to adsorption tube V1In 3
Charged pressure is p4Test gas；
(7) step, closes needle-valve 1 and opens needle-valve 2, by adsorption tube V13 and adsorption tube V22 connections, record pressure is p5；
(8) step, changes p4Value, repeat step (six) to step (7) 1-10 time, the corresponding p of record5；
(9) step, it is assumed that cold-zone temperature isCalculating obtains adsorption tube V13 and adsorption tube V13+ adsorption tubes V22 cold-zone
Volume accounts for the ratio between cumulative volumeWithRespectively
(10) step, test gas density is expressed as ρ ', calculates in different pressures p5It is lower to test obtained steel ball cumulative volume
ForWherein
MakeWith p5Change curve；
(11) step, changing cold-zone temperature isWherein i=1,2,3 ..., repeat step (nine) to step (10),
Suitable cold-zone temperature is found using dichotomySo that calculating what is obtainedWith actual value V0Close and basic and p5Value without
Close, then obtain cold-zone temperature
The step 3 leak detection step is as follows：
(1) step, Heated Copper coasting body heating furnace to test temperature T2And remain stable, to adsorption tube V13 and adsorption tube
V2Charged pressure is p in 21Test gas；
(2) step, closes needle-valve 1 and opens needle-valve 2, test 1-72 hour, p in the unit of account time1Variable quantity
(absolute value), is designated as slip δ.
Step 4 testing procedure is as follows：
(1) step, to adsorption tube V2It is m that quality is added in 2sTesting sample, holding meanss be in room temperature T0；
(2) step, switching three-way ball valve 5 causes needle-valve 1 to be connected with vavuum pump 4, opens needle-valve 1 and needle-valve 2, will adsorb
Pipe V13 and adsorption tube V22 are evacuated to vacuum；
(3) step, closes needle-valve 2, switching three-way ball valve 5 causes pressure-reducing valve 6 to be connected with needle-valve 1, to adsorption tube V1In 3
Charged pressure is p1Helium；
(4) step, closes needle-valve 1 and opens needle-valve 2, by adsorption tube V13 and adsorption tube V22 connections, record pressure is p2；
(5) step, calculating sample volume is
(6) step, by adsorption tube V13 and adsorption tube V22 are evacuated to vacuum, Heated Copper coasting body heating furnace to test temperature T2
And remain stable；
(7) step, closes needle-valve 2, switching three-way ball valve 5 causes pressure-reducing valve 6 to be connected with needle-valve 1, to adsorption tube V1In 3
Charged pressure is p3Test gas；
(8) step, closes needle-valve 1 and opens needle-valve 2, by adsorption tube V13 and adsorption tube V22 connections, record pressure is at any time
Between change p4(t)；
(9) step, it is assumed that pressure p4In t=t∞When tend towards stability, then can obtain adsorbent temperature be T2, pressure is p4
(t∞) when the true adsorption curve of HTHP beWherein Mg
To test the molal weight of gas.
(10) step, changes p3Size, it is T that repeat step seven to step 9, which can be obtained in temperature,2When different pressures under it is true
Real High Pressure Absorption curve.
Single-the 20mm of diameter 1 of standard steel ball, volumetric errors≤0.1%.
The test temperature T2For 200-1000K, test pressure p4(t∞) it is 0-10MPa.
The test gas includes carbon monoxide, carbon dioxide, oxygen, nitrogen, hydrogen, hydrogen sulfide, sulfur dioxide, carbonyl
Sulphur, alkane, formaldehyde, acetaldehyde, nitrogen oxides etc..
The testing sample be activated carbon, zeolite, silica gel, aluminum oxide, solid amine, sodium carbonate, hydrotalcite, the double salt of magnesium-based,
Lithium metasilicate, lithium zirconate, calcium oxide etc..
The addition quality m of the testing samplesIt should ensure that the pressure drop p in test process4(t0)-p4(t∞) it is no more than p4
(t0) 20%, but higher than pressure sensor detection resolution.
Embodiment 1
Demarcated, measured respectively to adsorption tube V using a diameter of 7mm steel ball2Not ball adding (V in 20=0), plus 100
Ball (V0=17.959mL), plus 200 ball (V0=35.919mL) when p1And p2Value, result of calculation is shown in Table 1.As shown in figure 3,
Linear regression is carried out to result, a=-0.0111, b=1.9815 is obtained, coefficient correlation is 1.Calculating obtains V1And V2Respectively
90.09mL and 88.42mL.
The High Pressure Absorption dynamics to activated carbon is tested at room temperature, and the activated carbon used is Taixi anthracite post
Shape activated carbon.First hunted leak before experiment, search gas is CO2, test temperature T2For 288.15K, pressure p1For 1.078MPa,
The leak detection time is 70h, and leak detection result is shown in Fig. 4.Analyze data can obtain slip δ for 0.05bar/h.
Because test temperature is room temperature, therefore the demarcation of hot-zone cold-zone need not be carried out.Test process adds quality msFor 7g
Activated carbon (demarcation obtain sample volume for 2.43mL), before test first by activated carbon at 120 DEG C drying 3h.Respectively in p3For
Tested under 0.786,1.331,1.913,2.468,3.238,3.838MPa, obtain corresponding p4(t∞) it is respectively 0.186,
0.395,0.661,0.946,1.401,1.805MPa, true High Pressure Absorption curve is shown in Fig. 5.
Table 1
Embodiment 2
Existed using hydrotalcite K-MG30 (Sasol Germany GmbH) is modified to potassium with the identical test device of embodiment 1
400 DEG C of high pressure CO2Adsorption dynamics adsorption kinetics expansion research.Room temperature T0For 288.15K.It is (total using 30 a diameter of 7mm standards steel balls
Volume is 5.388mL) carry out the demarcation of hot-zone cold-zone.To adsorption tube V13 and adsorption tube V2Helium pressure p is filled with 21For
1.114MPa, is warming up to T2(691.15K), obtains p2And p3Respectively 2.252MPa and 2.262MPa.Risen in calibration process
Warm curve is shown in Fig. 6.
In T2It is lower to adsorption tube V1Charged pressure p is distinguished in 34For 1.078,2.132,3.347MPa CO2, measurement obtains
Corresponding p5Respectively 0.575,1.149,1.826MPa.The demarcation of hot-zone cold-zone is carried out according to data above, 2 are the results are shown in Table.Through
Cross contrast and determine cold-zone temperature T1For 373.15K,For 0.319,For 0.291.
Test process adds quality msFor 11.9g K-MG30 (it is 4.42mL that demarcation, which obtains sample volume), test preceding first
By K-MG30 at 450 DEG C vacuum activating 4h.Respectively in p3To be carried out under 0.457,0.639,1.013,1.616,2.169MPa
Test, obtains corresponding p4(t∞) it is respectively 0.144,0.228,0.411,0.715,1.004MPa, true High Pressure Absorption curve
See Fig. 7.
Table 2
Technical scheme is described in detail above-described embodiment.It is apparent that the present invention is not limited being retouched
The embodiment stated.Based on the embodiment in the present invention, those skilled in the art can also make a variety of changes accordingly, but appoint
What is equal with the present invention or similar change belongs to the scope of protection of the invention.
Claims (10)
1. a kind of true High Pressure Absorption kinetic test device of adsorbent, it is characterised in that described device adds including copper coasting body
Hot stove (1), adsorption tube V2(2), adsorption tube V1(3), vavuum pump (4), tee ball valve (5), pressure-reducing valve (6), computer (7), needle-valve
1 (8), pressure sensor (9), needle-valve 2 (10)；Pressure-reducing valve (6) left end connects steel cylinder gas, and right-hand member connects tee ball valve (5)；It is described
Tee ball valve (5) separates two-way up and down, and upper road connects needle-valve 1 (8), pressure sensor (9) and needle-valve 2 (10) successively, and lower road connects very
Empty pump (4)；Measurement signal is transmitted to computer (7) and preserved by the pressure sensor (9)；The adsorption tube V1(3) and absorption
Pipe V2(2) needle-valve 1 (8) and needle-valve 2 (10) downstream are respectively connected to, and is positioned in copper coasting body heating furnace (1).
2. device according to claim 1, it is characterised in that the pressure sensor (9) is diffusion silicon type, deposition tube
Resistance type or capacitance-type, accuracy class≤0.5%FS, corresponding time≤1s, output signal is 4-20mA.
3. device according to claim 1, it is characterised in that the pressure of multiple different ranges is set in the range of 0-10MPa
Sensor (9).
4. a kind of true High Pressure Absorption kinetic test method of adsorbent, it is characterised in that methods described usage right requires 1-3
Any one described device, comprises the following steps：
Step 1. volumetric calibration；
Step 2. hot-zone cold-zone is demarcated；
Step 3. is hunted leak；
Step 4. is tested.
5. method according to claim 4, it is characterised in that
Volumetric calibration comprises the following steps described in step 1：
(1) step, holding meanss are in room temperature T0, and environment temperature remains stable during calibration；
(2) step, switching three-way ball valve (5) causes needle-valve 1 (8) to be connected with vavuum pump (4), opens needle-valve 1 (8) and needle-valve 2
(10), by adsorption tube V1And adsorption tube V (3)2(2) it is evacuated to vacuum；
(3) step, closes needle-valve 2 (10), switching three-way ball valve (5) causes pressure-reducing valve (6) to be connected with needle-valve 1 (8), to absorption
Pipe V1(3) charged pressure is p in11Helium；
(4) step, closes needle-valve 1 (8) and opens needle-valve 2 (10), by adsorption tube V1And adsorption tube V (3)2(2) connect, record pressure
Power is p12；
(5) step, changes p11Value, repeat step (two) to step (4) 1-10 time, the p corresponding to record12；
(6) step, inquiry helium is in the density p (p corresponding to each pressure spot11, T0) and ρ (p12, T0), and it is carried out linear
Return, obtainWherein k1 is fit slope；
(7) step, to adsorption tube V2Middle addition cumulative volume is V02Standard steel ball, repeat step (two) to step (6), gained
Pressure is designated as p21And p22, obtainWherein k2 is fit slope；
(8) step, changes and adds adsorption tube V2(2) volume of steel ball in, repeat step (seven) 1-10 times, obtains ki, i=1,2,
3 ..., to gained kiAnd V0iLinear regression is carried out, is obtainedWherein V01=0, then adsorption tube V1(3) and absorption
Pipe V2(2) volume is respectivelyV2=(b-1) V1, wherein a and ki are fit slope, and b is fitting intercept；
The demarcation of hot-zone cold-zone comprises the following steps described in step 2：
(1) step, to adsorption tube V2(2) the standard steel ball close with testing sample volume is inserted in, total volume meter is V0；
(2) step, in room temperature T0It is lower to adsorption tube V1And adsorption tube V (3)2(2) charged pressure is p in1Helium, close needle-valve 1
And needle-valve 2 (10) (8)；
(3) step, Heated Copper coasting body heating furnace to test temperature T2And remain stable, record now pressure data p2；
(4) step, opens needle-valve 2 (10), by adsorption tube V1And adsorption tube V (3)2(2) connect, record pressure is p3；
(5) step, switching three-way ball valve (5) causes needle-valve 1 (8) to be connected with vavuum pump (4), needle-valve 1 (8) is opened, by adsorption tube
V1And adsorption tube V (3)2(2) it is evacuated to vacuum；
(6) step, closes needle-valve 2 (10), switching three-way ball valve (5) causes pressure-reducing valve (6) to be connected with needle-valve 1 (8), to absorption
Pipe V1(3) charged pressure is p in4Test gas；
(7) step, closes needle-valve 1 (8) and opens needle-valve 2 (10), by adsorption tube V1And adsorption tube V (3)2(2) connect, record pressure
Power is p5；
(8) step, changes p4Value, repeat step (six) to step (7) 1-10 time, the corresponding p of record5；
(9) step, it is assumed that cold-zone temperature isCalculating obtains adsorption tube V1And adsorption tube V (3)1(3)+adsorption tube V2(2) cold
Area's volume accounts for the ratio between cumulative volumeWithRespectively
(10) step, test gas density is designated as ρ ', calculates in different pressures p5The lower obtained steel ball cumulative volume tested isWherein
MakeWith p5Change curve；
(11) step, changing cold-zone temperature isWherein i=1,2,3 ..., repeat step (nine) to step (10), use
Dichotomy finds suitable cold-zone temperatureSo that calculating what is obtainedWith actual value V0Close and basic and p5Value is unrelated,
Then obtain cold-zone temperature
Leak detection comprises the following steps described in step 3：
(1) step, Heated Copper coasting body heating furnace to test temperature T2And remain stable, to adsorption tube V1And adsorption tube V (3)2
(2) charged pressure is p in1Test gas；
(2) step, closes needle-valve 1 (8) and opens needle-valve 2 (10), test 1-72 hour, p in the unit of account time1Variable quantity
(absolute value), is designated as slip δ；
Test comprises the following steps described in step 4：
(1) step, to adsorption tube V2(2) it is m that quality is added insTesting sample, holding meanss be in room temperature T0；
(2) step, switching three-way ball valve (5) causes needle-valve 1 (8) to be connected with vavuum pump (4), opens needle-valve 1 (8) and needle-valve 2
(10), by adsorption tube V1And adsorption tube V (3)2(2) it is evacuated to vacuum；
(3) step, closes needle-valve 2 (10), switching three-way ball valve (5) causes pressure-reducing valve (6) to be connected with needle-valve 1 (8), to absorption
Pipe V1(3) charged pressure is p in1Helium；
(4) step, closes needle-valve 1 (8) and opens needle-valve 2 (10), by adsorption tube V1And adsorption tube V (3)2(2) connect, record pressure
Power is p2；
(5) step, calculating sample volume is
(6) step, by adsorption tube V1And adsorption tube V (3)2(2) vacuum, Heated Copper coasting body heating furnace to test temperature T are evacuated to2
And remain stable；
(7) step, closes needle-valve 2 (10), switching three-way ball valve (5) causes pressure-reducing valve (6) to be connected with needle-valve 1 (8), to absorption
Pipe V1(3) charged pressure is p in3Test gas；
(8) step, closes needle-valve 1 (8) and opens needle-valve 2 (10), by adsorption tube V1And adsorption tube V (3)2(2) connect, record pressure
Power changes with time p4(t)；
(9) step, it is assumed that pressure p4In t=t∞When tend towards stability, then can obtain adsorbent temperature be T2, pressure is p4(t∞)
When the true adsorption curve of HTHP be
Wherein
MgFor rubbing for test gas
That quality；
(10) step, changes p3Size, it is T that repeat step (seven) to step (9), which can be obtained in temperature,2When different pressures under it is true
Real High Pressure Absorption curve.
6. method according to claim 5, it is characterised in that：The single diameter of standard steel ball of (seven) step in the step 1
1-20mm, volumetric errors≤0.1%.
7. method according to claim 5, it is characterised in that：In the step 4 (one) step testing sample include activated carbon,
Zeolite, silica gel, aluminum oxide, solid amine, sodium carbonate, hydrotalcite, magnesium-based double salt, lithium metasilicate, lithium zirconate, calcium oxide.
8. method according to claim 5, it is characterised in that：(1) step testing sample adds quality m in the step 4sShould
Ensure the pressure drop p in test process4(t0)-p4(t∞) it is no more than p4(t0) 20%, but higher than pressure sensor resolution.
9. method according to claim 5, it is characterised in that：The step 2 is to the test temperature T described in step 42For
The test pressure p of (nine) step in 200-1000K, step 44(t∞) it is 0-10MPa.
10. method according to claim 5, it is characterised in that：The test gas of (seven) step includes an oxygen in the step 4
Change carbon, carbon dioxide, oxygen, nitrogen, hydrogen, hydrogen sulfide, sulfur dioxide, cos, alkane, formaldehyde, acetaldehyde or nitrogen oxides.
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