1、Designation: D4780 12 (Reapproved 2017)1Standard Test Method forDetermination of Low Surface Area of Catalysts andCatalyst Carriers by Multipoint Krypton Adsorption1This standard is issued under the fixed designation D4780; the number immediately following the designation indicates the year oforigin
2、al adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1NOTESubsesction 8.1 was corrected editorially in February 2017.1. Scope1.1 T
3、his test method covers the determination of the specificsurface area of catalysts and catalyst carriers in the range from0.05 to 10 m2/g. A volumetric measuring system is used toobtain at least three data points which fall within the linear BETregion.1.2 The values stated in SI units are to be regar
4、ded asstandard. No other units of measurement are included in thisstandard.1.3 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determin
5、e the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D3663 Test Method for Surface Area of Catalysts andCatalyst CarriersD3766 Terminology Relating to Catalysts and CatalysisE177 Practice for Use of the Terms Precision and Bias inASTM Test MethodsE45
6、6 Terminology Relating to Quality and StatisticsE691 Practice for Conducting an Interlaboratory Study toDetermine the Precision of a Test Method3. Terminology3.1 DefinitionsConsult Terminology D3766.3.2 Symbols:PH1= initial helium pressure, torr.PH2= helium pressure after equilibration, torr.TH1= te
7、mperature of manifold at initial heliumpressure, C.TH2= temperature of manifold after equilibration, C.P1= initial Kr pressure, torr.T1= manifold temperature at initial Kr pressure, K.T1= manifold temperature at initial Kr pressure, C.P2= Kr pressure after equilibration, torr.T2= manifold temperatur
8、e at P2,K.T2= manifold temperature at P2, C.Po,N= liquid nitrogen vapor pressure, torr.Po,krypton= calculated krypton vapor pressure, torr.Ts= liquid nitrogen temperature, K.X = relative pressure, P2/Po,krypton.Vd= volume of manifold, cm3.Vs= the apparent dead-space volume, cm3.Ws= weight of sample,
9、 g.W1= tare weight of sample tube, g.W2= weight of sample plus tare weight of tube, g.Vds= volume of krypton in the dead space, cm.3V1= See 11.3.5.V2= See 11.3.6.Vt= See 11.3.7.Va= See 11.3.9.Vm= See 11.6.4. Summary of Test Method4.1 A catalyst or catalyst carrier sample is degassed byheating in vac
10、uum to remove absorbed vapors from thesurface. The quantity of krypton adsorbed at various lowpressure levels is determined by measuring pressure differen-tials after introduction of a fixed volume of krypton to thesample at liquid nitrogen temperature.The specific surface areais then calculated fro
11、m the sample weight and adsorption datausing the BET equation.5. Significance and Use5.1 This test method has been found useful for the determi-nation of the specific surface area of catalysts and catalystcarriers in the range from 0.05 to 10 m2/g for materials1This test method is under the jurisdic
12、tion of ASTM Committee D32 onCatalysts and is the direct responsibility of Subcommittee D32.01 on Physical-Chemical Properties.Current edition approved Feb. 1, 2017. Published February 2017. Originallyapproved in 1988. Last previous edition approved in 2012 as D478012). DOI:10.1520/D4780-12R17.2For
13、referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700,
14、West Conshohocken, PA 19428-2959. United StatesThis international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recommendations issued by the World
15、 Trade Organization Technical Barriers to Trade (TBT) Committee.1specification, manufacturing control, and research and devel-opment in the evaluation of catalysts. The determination ofsurface area of catalysts and catalyst carriers above 10 m2/g isaddressed in Test Method D3663.6. Apparatus6.1 Asch
16、ematic diagram of the apparatus is shown in Fig. 1.It may be constructed of glass or of metal and may operatemanually or automatically. It has the following features:6.1.1 Vacuum System, capable of attaining pressures below10-4torr (1 torr = 133.3 Pa). This will include a vacuum gage(not shown in Fi
17、g. 1). Access to the distribution manifold isthrough the valve V.6.1.2 Distribution Manifold, having a volume between 5and 40 cm3(Vd) known to the nearest 0.01 cm3. This volumeis defined as the volume between the stopcocks or valves andit includes the volume within the pressure gage.6.1.3 Constant V
18、olume Gages, capable of measuring 1 to 10torr to the nearest 0.001 torr and 0 to 1000 torr to the nearesttorr (1 torr = 133.3 Pa).6.1.4 Valve (H), from the helium supply to the distributionmanifold.6.1.5 Valve (K), from the krypton supply to the distributionmanifold.6.1.6 Sample Tube(s), with volume
19、 between 5 cm3and 25cm3, depending on the application. The sample tube(s) may beconnected to the distribution manifold with standard taperjoints, glass-to-glass seals, or compression fittings.NOTE 1Modern commercial instruments may employ simple tubeswith volumes outside of this range, and may be ca
20、pable of testing multiplesamples simultaneously rather than separately as stated in 9.1.6.1.7 Dewar Flask(s) for immersion of the sample tube(s) inliquid nitrogen. The nitrogen level should be fixed at a constantheight by means of an automatic level controller or manuallyrefilled to a predetermined
21、mark on the sample tube(s) about 30to 50 mm below the distribution manifold connectors.6.1.8 Thermometer for measuring the temperature of thedistribution manifold (T1(i)orT2(i) in degrees Celsius.(Alternatively, the distribution manifold may be thermostatteda few degrees above ambient to obviate the
22、 necessity ofrecording this temperature.)6.1.9 Heating Mantle(s) or Small Furnace(s) for eachsample tube to allow outgassing samples at elevated tempera-tures.6.1.10 Laboratory Balance with 0.1 mg (107kg) sensitiv-ity.6.1.11 Thermometer for measuring the temperature of theliquid nitrogen bath (Ts(i)
23、 in kelvins. This will preferably bea nitrogen vapor-pressure-thermometer that gives Po,Ndirectlyand has greater precision, or a resistance thermometer fromwhich Po,Nvalues may be derived.7. Reagents7.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated,
24、it is intended thatall reagents shall conform to the specifications of the Commit-tee on Analytical Reagents of the American Chemical Society,where such specifications are available.3Other grades may beused, provided it is first ascertained that the reagent is ofsufficiently high purity to permit it
25、s use without lessening theaccuracy of the determination.7.2 Helium Gas, at least 99.9 % pure.7.3 Krypton Gas, at least 99.9 % pure.7.4 Liquid Nitrogen, of such purity that the saturation vaporpressure Po,Nis not more than 20 torr above barometricpressure. A fresh daily supply is recommended.8. Proc
26、edureSample Preparation and Degassing8.1 Select a sample tube of the desired size. A 5 cm3tube ispreferred for small samples to minimize dead space. However,larger tubes may be required for larger samples or for finelypowdered samples, to avoid elutriation of the powder whendegassing is started.8.2
27、Evacuate the sample tube and then fill to atmosphericpressure with helium. This may be done on the surface areaunit, or on a separate piece of equipment.8.3 Remove the sample tube, cap, and weigh. Record theweight as W1.8.4 Place the sample, whose weight is knownapproximately, into the sample tube.
28、If possible, choose thesample size to provide an estimated total surface area of 1 to 5m2.8.5 Attach the sample tube to the apparatus. If other samplesare to be run, attach them at this time to the other ports.8.6 Open the S valves where there are samples.8.7 Slowly open the V valve, monitoring the
29、rate of pressuredecrease to avoid too high a rate, which might lead to excessivefluidization of powdered samples.8.7.1 If a diffusion pump is used, it may be necessary toclose the V valve system periodically to protect the diffusionpump fluid from exposure to pressures above 0.1 torr forperiods of m
30、ore than 30 s. Close the valve off for 2 min eachtime.3Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For Suggestions on the testing of reagents notlisted by the American Chemical Society, see Annual Standards for LaboratoryChemicals, BDH Ltd.,
31、 Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.FIG. 1 Schematic Diagram of Surface Area ApparatusD4780 12 (2017)128.8 Install a heating mantle or furnace around each sampleand raise the temperature to about 300
32、C (573 K). (WarningTake special precautions if the moisture content exceedsapproximately 5 % to avoid “bumping” of powdered catalyst,and to avoid surface area loss by self-steaming. It is recom-mended that the heating rate not exceed 100 K/h under thesecircumstances.)8.9 Continue degassing at about
33、300C (573 K) for aminimum of 3 h, at a pressure not to exceed 103torr.Overnight degassing is permissible.NOTE 2Certain materials decompose or sinter at 300C. Lowerdegassing temperatures are permissible for such materials; however, thedegassing temperature should be specified when reporting the resul
34、ts.8.10 Remove the heating mantles, and allow the samples tocool.8.11 Close the S valves.8.12 It is permissible to exercise the option of preliminarydegassing on an external unit. In such a case, follow theprocedures of 8.4 8.11 and then repeat on the adsorption unit,except that the degassing on the
35、 adsorption unit can be at roomtemperature and need not exceed 1 h.8.13 If it is desired to weigh the sample after preliminarydegassing on an external unit, backfill with helium to slightlyabove atmospheric pressure. Close the S valve.8.13.1 Detach the sample tube from the apparatus, recapwith the s
36、topper used previously, and weigh. Record the weightas W2.8.13.2 Reattach the sample tube to the apparatus. Removethe backfilled gas by evacuation to less than 103torr at roomtemperature. This should normally take 5 to 10 min.9. ProcedureDead-Space Determination9.1 From this point on, each sample be
37、ing tested for kryptonadsorption shall be run on an individual basis. Thus, 9.1 10.12 shall be carried out separately for each tube in test.9.2 The dead space is the void volume of the chargedsample tube, including the volume within the S valve, when thetube is immersed in liquid nitrogen to the pro
38、per depth.9.3 Place a Dewar flask of liquid nitrogen around the sampleand adjust the liquid level to a fixed point on the sample tube.Maintain this level through the test.9.4 Zero the pressure gage, if needed.9.5 Admit the helium gas into the system to a pressure of600 to 900 torr by carefully openi
39、ng the H valve. Record thispressure, PH1, and the manifold temperature, TH1.9.6 Open the S valve to admit helium to the sample.9.7 After about 5 min of equilibration, readjust the liquidnitrogen level (if needed), and record the pressure, PH2andmanifold temperature, TH2.9.8 Repeat 9.5 9.7 for each s
40、ample cell attached to themanifold.9.9 Open all S valves, then slowly open the V valve toremove the helium gas.9.10 Close the S valve when a pressure below 103torr hasbeen attained. This should normally take 5 to 10 min.10. ProcedureKrypton Adsorption10.1 Close the V valve.10.2 Admit krypton gas by
41、opening the K valve and recordpressure as P1(1) and temperature as T1(1). (It is desirable tochoose P1(1) such that P2(1)/Po(1) is about 0.05.)10.3 Open the S valve to admit krypton to the sample.10.4 Allow sufficient time for equilibration, readjusting theliquid nitrogen level periodically if neede
42、d. Equilibrium shallbe considered as attained when the pressure changes by nomore than 0.001 torr in 5 min.10.5 Record the equilibrium pressure, P2(1), and manifoldtemperature, T2(1).10.6 Record the liquid nitrogen temperature Ts(1) or thenitrogen vapor pressure Po,N(1).10.7 Close the S valve.10.8 R
43、epeat 10.2 10.7 until there are at least three pointsin the linear BET region (P2/Po,krypton= 0.05 to 0.30). Desig-nate the pressures, manifold temperatures, liquid nitrogen bathtemperatures or nitrogen vapor pressures as P1(i), P2(i), T1(i),T2(i), Ts(i), and Po,N(i) respectively for each ith iterat
44、ion (i=2ton, where n is the total number of points).NOTE 3The quantity of krypton gas admitted at each adsorption pointin step 10.2 depends on the manifold volume, possible dosing system,dead space, and sample surface area. It is recommended that small kryptondoses be used initially to ensure that a
45、t least three equilibration points areobtained in the linear BET region.10.9 Open the S valve, slowly open the V valve, remove theDewar flask, and allow the sample tube to warm to roomtemperature.10.10 When frost has disappeared from the sample tube,wipe it dry.10.11 Backfill the sample tube with he
46、lium to atmosphericpressure or slightly above. Close the S valve.10.12 Detach the sample tube from the apparatus, recapwith the stopper used previously, and weigh. Record the weightas W2. If the sample was previously weighed followingdegassing, this step may be omitted.11. Calculation11.1 Calculate
47、the weight of sample Wsas follows:Ws5 W22 W1(1)11.2 Calculate the dead space Vsas follows:Vs5TsVdPH23FPH1TH11273.22PH2TH21273.2G(2)11.3 For each point, i = 1, 2 ., n, calculate the following:11.3.1 If Po,N(i) is not measured directly, the values of Ts(i)can be converted to Po,N(i) by the following e
48、quation for 76 Ts(i) 80:In Po,Ni!/2549.78 5 Ax1Bx3/21Cx31Dx6#/1 2 x! (3)where:D4780 12 (2017)13X = (1Ts/126.2),A = 6.09676,B = 1.1367,C = 1.04072, andD = 1.93306 (1).411.3.2 Saturation vapor pressure of krypton Po,krypton(i):Po,kryptoni! 5 exp1.919 In Po,Ni! 2 11.82# (4)NOTE 4The above calculation o
49、f Po,krypton(i) is based on the use of theClausius-Clapeyron equation to extrapolate the vapor pressure of liquidkrypton to liquid nitrogen temperature (2, 3). Other methods have beenreported in the literature or are used on commercially available instru-mentation. These methods are acceptable, but should be identified in thereport.11.3.3 X i!5relative pressure5P2i!/Po,kryptoni!11.3.4 Manifold temperature in:T1i! 5 T1i!1273.2 (5)T2i! 5 T2i!1273.211.3.5 The krypton volume in the manifold (and dosingsystem) before equi
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