CN104020261B - A kind of detecting catalyst optionally method - Google Patents
A kind of detecting catalyst optionally method Download PDFInfo
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- CN104020261B CN104020261B CN201410276292.1A CN201410276292A CN104020261B CN 104020261 B CN104020261 B CN 104020261B CN 201410276292 A CN201410276292 A CN 201410276292A CN 104020261 B CN104020261 B CN 104020261B
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- carburizing
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- catalyst
- catalyzer
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- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000005255 carburizing Methods 0.000 claims abstract description 25
- 238000012360 testing method Methods 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 9
- 238000011056 performance test Methods 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 238000011065 in-situ storage Methods 0.000 claims 1
- 238000011156 evaluation Methods 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract 2
- 229910052742 iron Inorganic materials 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000007789 gas Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZXKXJHAOUFHNAS-FVGYRXGTSA-N (S)-fenfluramine hydrochloride Chemical compound [Cl-].CC[NH2+][C@@H](C)CC1=CC=CC(C(F)(F)F)=C1 ZXKXJHAOUFHNAS-FVGYRXGTSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Abstract
A kind of detecting catalyst optionally method, the object of alternative traditional evaluating catalyst method is reached by the mode of the carburizing performance of testing sample catalyst, basic step comprises three programs, program one, catalytic reaction evaluation is carried out to known catalysts sample, obtains its selectivity S ' to low-carbon alkene; Program two, carries out carburizing performance test to unknown catalyzer and known catalysts respectively, obtains peak height H and H ' at the CO consumption peak that carburizing curve in each comfortable 365 DEG C to 455 DEG C temperature ranges is formed; Program three, utilizes relational expression S/S '=H/H ', obtains the selectivity S of unknown catalyzer to low-carbon alkene.The method is particularly useful for evaluating the selectivity of iron catalyst to low-carbon alkene in F-T synthesis.
Description
Technical field
The present invention relates to a kind of method of detecting catalyst, be specifically related to a kind ofly test metallic catalyst method to C2 to C4 olefine selective in Fischer-Tropsch synthesis.
Background technology
F-T synthesis is with CO and H
2for unstripped gas, under the effect of catalyzer, synthesis has the reaction of different carbon chain structured product.Dissimilar catalyzer has obvious performance difference in Fischer-Tropsch synthesis, this species diversity is mainly manifested in the selectivity of reaction product, such as pure Fe catalyzer, saturated hydro carbons mostly is in its Fischer-Tropsch synthetic, and with the addition of K or Mn as after auxiliary agent, in catalytic reaction products, the content of unsaturated hydro carbons significantly improves.
Traditional fischer-tropsch synthetic catalyst test evaluation method is placed in reaction tube by a certain amount of catalyst sample, first passes into H
2at a certain temperature catalyst sample is reduced, then using the different H as reaction raw materials
2the synthetic gas of/CO ratio passes into reactor, under certain reaction conditions, through the catalyzed conversion effect of catalyzer, generate the product of different structure, by these products by the instrument monitoring such as chromatogram, mass spectrum analysis composition content, draw the reactivity worth result comprising selectivity of this catalyst sample through data preparation.Due to the existence of decomposition induction time, the catalytic performance data obtained within induction period are not the true reflections of catalyst performance, and therefore traditional evaluation response time at least will more than 10 hours, and the reaction result data of the sample obtained like this are just substantially credible.This shows, be a process very consuming time by classic method evaluate catalysts.In order to improve the efficiency of evaluating catalyst process, the invention provides a kind of can Fast Evaluation catalyzer to the method for selectivity of light olefin, the method, be utilize test sample carburizing performance quick obtaining sample choice.So-called carburizing performance is because metallics in catalyzer is different from the chemical action between CO molecule, and catalyst sample along with temperature variation, can show different CO and consume trend in CO atmosphere.The time of carburizing test generally can not more than 90 minutes, and evaluation time time less than traditional at least 10 substantially reduces.
Summary of the invention
The object of the present invention is to provide one can detecting catalyst in Fischer-Tropsch synthesis to low-carbon alkene (namely ethene, propylene and butylene and isomeride thereof) optionally method, by the unknown catalyst sample of comparison and known catalysts in carburizing test, carburizing curve in 365 DEG C to 455 DEG C warm areas forms CO and consumes the high relation of peak-to-peak, obtains unknown catalyst sample fast to the selectivity of low-carbon alkene.
A kind of detecting catalyst provided by the invention is to the method for selectivity of light olefin, and basic step comprises three programs below, and program one, carries out catalytic reaction evaluation to known catalysts sample, obtains its selectivity S ' to low-carbon alkene; Program two, carries out carburizing performance test to unknown catalyzer and known catalysts respectively, obtains peak height H and H ' at the peak that carburizing curve is formed in each comfortable 365 DEG C to 455 DEG C temperature ranges; Program three, utilizes relational expression S/S '=H/H ', obtains the selectivity S of unknown catalyzer to low-carbon alkene.
Concrete, program one, be the process of known catalyst sample being carried out to catalytic reaction evaluation, concrete operations condition is as follows, takes the catalyzer of 0.1g to 10g, at 300 DEG C to 500 DEG C, under pressure 0MPa to 5MPa, uses H
2reduce 1 little of 5 hours, then gas is switched to H
2the synthetic gas of/CO=3, at pressure 2MPa to 6MPa, by the volume of the reactant of per volume of catalyst in the volume space velocity GHSV(unit interval) 200hr
-1to 10000hr
-1, react at temperature of reaction 200 DEG C to 500 DEG C, react after more than 10 hours, adopt the content of each component in gas chromatographic detection assay products, low-carbon alkene (alkene of C2 to C4) selectivity S ' (by weight percentage)=(∑ C
n =)/(∑ C
nh
2n+2+ ∑ C
nh
2n), n=2 here, 3,4.
Program two carries out carburizing performance test to unknown catalyzer and known catalysts respectively, obtains peak height H and H ' at the peak that carburizing curve is formed in each comfortable 365 DEG C to 455 DEG C temperature ranges.The process of carburizing test is 200 DEG C to 600 DEG C, under 0MPa to 5MPa, use H
2by little for sample preparation 1 after 4 hours, H
2after being cooled to room temperature in atmosphere, switch to the CO gas (CO accounts for 0.1% to 20% of cumulative volume) of inert gas dilution by catalyst sample bed, flow control is at 1mLmin
-1g
-1catalyzer is to 20mLmin
-1g
-1in range of catalysts, start to heat up to catalyst sample simultaneously, the speed heated up is 1 DEG C/min to 20 DEG C/min, with the detecting device of on-line checkingi CO content detecting the consumption of CO under different temperatures, being formed with temperature is horizontal ordinate, the carburizing curve that the CO signal intensity detected with instrument is ordinate, and the detecting device of on-line checkingi CO content can be thermal conductivity detector (TCD), mass detector, infrared detector.
Program three, the S ', H and H ' that obtain in program one and program two substitute into relational expression S/S '=H/H ', calculate the selectivity S of unknown catalyzer to low-carbon alkene.
Said process completes on the same hardware platform, and this platform comprises, induction system, reactive system, reaction product testing and analysis system; In induction system, different media flows in different pipelines, controls the flow of gas with different mass-flow gas meters, controls and conveying liquid with volume pump; Reactive system comprises, reaction member and the unit that reaction institute energy requirement is provided of loading catalyst sample, reaction member can be single pass, also can be multichannel, the manufacture material of reaction member can be metal, also can be quartzy, the energy supply form providing the unit of reaction institute energy requirement can be Resistant heating, Elema heats, and also can be microwave energy supply, plasma energy supply; Reaction product testing and analysis system comprises can the detector system of product composition that flows out from reaction member of on-line checkingi and corresponding data collection analysis system, and detection system can be chromatographic detector, mass detector, infrared detector.
Accompanying drawing explanation
Fig. 1 is the carburizing curve of test known sample HA202Q.
Embodiment
Below in conjunction with drawings and Examples, the present invention is further detailed.
The following examples only for explaining explanation the present invention in detail, and limit the scope of the invention never in any form.
Embodiment 1
First, evaluate known catalyst sample, it is a kind of commercially available synthetic ammonia catalyst HA202Q(Pingxiang City Parkson chemical filler company limited), take this catalyst sample of 1g, at 400 DEG C, under 2.5MPa, use H
2reduce 3 hours, then gas is switched to H
2the synthetic gas of/CO=3, at pressure 3MPa, volume space velocity GHSV=800hr
-1, react at temperature of reaction 320 DEG C, reaction 12 is constantly little, adopts the content of each component in gas chromatographic detection assay products, low-carbon alkene (alkene of C2 to C4) selectivity S '=45.3%
Then, be that carburizing performance test is carried out to HA202Q, take this sample of 1g, 400 DEG C, under 2MPa, use H
2reductase 12 hour, H
2be cooled to room temperature in atmosphere, by catalyst sample bed, flow control is at 10mLmin for the CO gas (CO accounts for 10% of cumulative volume) then switching to inert gas dilution
-1g
-1catalyzer, start to heat up to catalyst sample simultaneously, the speed heated up is 10 DEG C/min, the CO content flowed out in reaction member is detected with online mass detector (Omnistar300), formed as the carburizing curve of Fig. 1, the peak that carburizing curve is formed in 365 DEG C to 455 DEG C temperature ranges is if the peak P in Fig. 1, peak maximum P are to this length of line segment PK and peak height H ' between subpoint K on baseline WE, according to the data result of test, H '=4.0 × 10
-11ev.
Subsequently, being carry out carburizing performance test to unknown catalyzer, is the same (selecting the HTA206 ammonia synthesis catalyst of Liaoning Haitai development in science and technology company limited here as unknown catalyzer) when test condition and test HA202Q.The carburizing curve that test obtains formed in 365 DEG C to 455 DEG C temperature ranges CO consume peak height H=4.3 × 10 at peak
-11ev.
Finally, according to relational expression S/S '=H/H ', unknown catalyzer (HTA206) can be obtained in Fischer-Tropsch synthesis to the selectivity S=of low-carbon alkene (H/H ') × S '=48.7%.
Claims (1)
1. a detecting catalyst optionally method, be specially a kind of for testing catalyzer in F-T synthesis producing olefinic hydrocarbons process to the optionally method of carbon two to the low-carbon alkene of carbon four, it is characterized in that, by the carburizing performance of the sample of the unknown catalyzer of comparison and known catalytic performance, obtain the result of unknown catalyst choice S, concrete grammar is as follows
First carry out carburizing performance test, form unknown catalyzer and known catalysts carburizing curve separately, operation steps is as follows, the first step, carries out H to catalyst sample
2reduction treatment; Second step, with containing CO gas in the first step by H
2the sample in-situ of reduction treatment carries out Carburization Treatment, simultaneously the consumption of CO under on-line checkingi different temperatures, and being formed with temperature is horizontal ordinate, the carburizing curve that the CO signal intensity detected with instrument is ordinate;
Then, with the peak height at the peak formed in 365 DEG C to 455 DEG C temperature ranges in the carburizing curve of unknown catalyzer and known catalysts for comparison other, the peak height that unknown catalyst sample is formed is H, the peak height of known catalytic performance sample is H ', meets relational expression S/S '=H/H ' between the selectivity S of unknown catalyst sample and known sample selectivity S '.
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|---|---|---|---|
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|---|---|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106841294B (en) * | 2017-01-26 | 2019-05-28 | 王宏铭 | A kind of method of differential thermal analysis evaluation catalytic performance |
| CN106841293B (en) * | 2017-01-26 | 2019-05-28 | 王宏铭 | A method of catalyst is evaluated using difference quotient thermogravimetric |
| CN106802262B (en) * | 2017-01-26 | 2019-05-28 | 王宏铭 | A method of catalyst performance is tested using thermogravimetry |
| CN106770452B (en) * | 2017-01-26 | 2019-05-28 | 王宏铭 | A method of catalyst is evaluated using thermal analysis system |
| CN110361499A (en) * | 2018-04-09 | 2019-10-22 | 国家能源投资集团有限责任公司 | The method of iron-base fischer-tropsch synthesis catalyst activity rating |
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|---|---|---|---|---|
| US4468474A (en) * | 1983-05-16 | 1984-08-28 | Allied Corporation | Iron/silicon-based catalyst exhibiting high selectivity to C2 -C62 Fischer-Tropsch reactions |
| US4554291A (en) * | 1983-05-16 | 1985-11-19 | Allied Corporation | Iron/silicon-based catalyst exhibiting high selectivity to C2 -C62 Fischer-Tropsch reactions |
| US20140065059A1 (en) * | 2010-12-08 | 2014-03-06 | Sumitomo Chemical Company, Limited | Catalyst for producing an olefin from an alcohol, method for producing olefin, polyolefin, and olefin oxide |
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