CN108509763B - Method for evaluating activity of carbon deposition catalyst - Google Patents
Method for evaluating activity of carbon deposition catalyst Download PDFInfo
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- CN108509763B CN108509763B CN201810308831.3A CN201810308831A CN108509763B CN 108509763 B CN108509763 B CN 108509763B CN 201810308831 A CN201810308831 A CN 201810308831A CN 108509763 B CN108509763 B CN 108509763B
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- G16C20/00—Chemoinformatics, i.e. ICT specially adapted for the handling of physicochemical or structural data of chemical particles, elements, compounds or mixtures
- G16C20/30—Prediction of properties of chemical compounds, compositions or mixtures
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Abstract
The invention discloses a method for evaluating the activity of a catalyst. The catalyst carbon deposit amount is one of the parameters for evaluating the activity of the catalyst, and the catalyst carbon deposit amount is usually measured by adopting an oxygen-introducing combustion mode, so that the operation is complex, and the structure and the performance of the catalyst are partially damaged due to the heat release of combustion. Based on the fact that the carbon deposit contains free radicals which can be measured by paramagnetic resonance and the concentration of the free radicals is in proportional relation with the carbon deposit amount of the catalyst, the carbon deposit amount of the catalyst can be estimated by measuring the concentration of the free radicals on the catalyst, and then the activity of the catalyst is evaluated. The invention is characterized by simple and easy operation without changing the structure and performance of the catalyst. The invention is suitable for evaluating the activity of various carbon deposition catalysts.
Description
Technical Field
The present invention relates to a method for evaluating the activity of a catalyst, and particularly to a method for evaluating the activity change of a catalyst caused by carbon deposition.
Background
The activity of the catalyst used in the oil refining chemical process gradually decreases partly because of carbon deposition caused by the reaction of the raw materials on the surface of the catalyst, and the carbon deposition is generally insoluble in many solvents, such as toluene, chlorobenzene, carbon disulfide, tetrahydrofuran, and the like. The carbon deposition process involves the condensation polymerization of free radicals, and some of the unpaired electrons are bound or embedded in the carbon to form stable free radicals measurable by paramagnetic resonance spectroscopy (ESR). Research shows that the free radical concentration measured by ESR in a certain carbon deposit range and the carbon deposit amount on the catalyst present a proportional relation.
The commercial evaluation of catalyst activity involves comparing the conversion of the feedstock at a fixed space velocity or the temperature required to achieve the same conversion. In the course of the catalytic reaction, the decrease in the catalyst activity is accompanied by an increase in the amount of coke deposited, and therefore the amount of coke deposited on the catalyst is frequently used industrially as a parameter for evaluating the catalyst activity. The carbon deposit amount is generally measured by oxygen-introducing combustion, and the carbon deposit amount of the catalyst can be obtained from the mass of carbon dioxide after combustion or the mass difference of the catalyst before and after combustion.
Disclosure of Invention
The invention provides a simple method for evaluating the evaluation activity of a carbon deposition catalyst, which evaluates the activity of the catalyst by directly measuring the change of the concentration of free radicals in the carbon deposition catalyst, because the carbon deposition amount of the catalyst is a parameter for representing the activity of the catalyst and the proportional relationship exists between the carbon deposition amount of the catalyst and the concentration of the free radicals.
The technical scheme of the invention is as follows: and respectively measuring the free radical concentration of the fresh catalyst and the completely deactivated catalyst, taking the free radical concentrations as two limit values of the catalyst activity, comparing the free radical concentration of the carbon deposition catalyst to be measured with the free radical concentrations, and evaluating the carbon deposition catalyst activity according to a formula 1.
Wherein: a. thecIs a catalyst activity parameter;
Ncis the carbon deposit catalyst free radical concentration;
N0is the fresh catalyst radical concentration;
Ndis the radical concentration of the completely deactivated catalyst.
Two parameters of g value and line width can be obtained in the process of measuring free radicals, and the two parameters can be used for researching the structural information of carbon deposit on the catalyst.
The catalyst described in the above scheme may be any type of carbon deposit catalyst, but it is required that the carbon deposit formation process involves a radical reaction, and the carbon deposit contains radicals.
The method has the advantages of simple operation, high activity evaluation accuracy and no damage to the catalyst structure.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
[ example 1]
NiMo/gamma-Al catalyst for hydrogenation of industrial residue fixed bed with different running times2O310 mg was charged into a glass tube having an inner diameter of 3 mm and a length of 35 mm, the interior of the glass tube was purged with nitrogen gas for 60 seconds to remove oxygen from the glass tube, and then sealed. And (4) placing the sealed glass tube into a paramagnetic tube, and measuring the concentration of free radicals of the carbon-deposited catalyst by adopting a paramagnetic resonance instrument. Meanwhile, the sulfurized fresh catalyst NiMo/gamma-Al2O3And a completely deactivated catalyst NiMoγ-Al2O3(char formation 18.7%) the radical concentration was measured by the above-mentioned method. The catalyst activity (expressed as the average bed temperature), the amount of coke deposited and the concentration of free radicals are shown in Table 1. As can be seen from the table, as the reaction time increases, the bed temperature of the residual oil hydrogenation catalyst gradually increases, the carbon deposition amount gradually increases, and the concentration of the free radicals gradually increases.
[ example 2]
Hydrogenation catalyst NiMoP/gamma-Al for industrial coal tar with different running times2O310 mg was charged into a glass tube having an inner diameter of 3 mm and a length of 35 mm, and the inside of the glass tube was purged with nitrogen gas for 60 seconds to discharge oxygen gas from the glass tube, followed by sealing. And (4) placing the sealed glass tube into a paramagnetic tube, and measuring the concentration of free radicals of the carbon-deposited catalyst by adopting a paramagnetic resonance instrument. Simultaneously, the sulfurized fresh catalyst NiMoP/gamma-Al2O3And a completely deactivated catalyst NiMoP/gamma-Al2O3(carbon deposition amount: 15.6%) the radical concentration was measured by the above-mentioned method. The catalyst activity (expressed as the average bed temperature), the amount of coke deposited and the concentration of free radicals are shown in Table 2. As can be seen from the table, the temperature of the bed layer of the coal tar hydrogenation catalyst gradually increases with the increase of the reaction time, the carbon deposition amount gradually increases, and the concentration of the free radicals gradually increases.
[ example 3]
The industrial diesel oil hydrogenation catalyst NiMoW/gamma-Al with different running times2O310 mg was charged into a glass tube having an inner diameter of 3 mm and a length of 35 mm, the interior of the glass tube was purged with nitrogen gas for 60 seconds to remove oxygen from the glass tube, and then sealed. And (4) placing the sealed glass tube into a paramagnetic tube, and measuring the concentration of free radicals of the carbon-deposited catalyst by adopting a paramagnetic resonance instrument. Simultaneously, the sulfurized fresh catalyst NiMoW/gamma-Al2O3And a completely deactivated catalyst NiMoW/gamma-Al2O3(char formation 9.4%) the radical concentration was measured by the above-mentioned method. The catalyst activity (expressed as the average bed temperature), the amount of coke deposited and the concentration of free radicals are shown in Table 3. As can be seen from the table, the bed temperature of the diesel hydrogenation catalyst gradually increases and accumulates with the increase of the reaction timeThe carbon amount gradually increases and the concentration of free radicals gradually increases.
Table 1 change in activity during residuum hydrogenation catalyst reaction
TABLE 2 Change in Activity during reaction of coal tar hydrogenation catalyst
TABLE 3 Activity Change during Diesel hydrogenation catalyst reaction
Claims (3)
1. A method for evaluating the activity of a catalyst containing soot, characterized in that a catalyst activity parameter is obtained by using the following formula to evaluate the catalyst activity:
wherein: a. thecIs a catalyst activity parameter; n is a radical ofcIs the carbon deposit catalyst free radical concentration; n is a radical of0Is the fresh catalyst radical concentration; n is a radical ofdIs the radical concentration of the completely deactivated catalyst.
2. The method of claim 1 wherein the free radical concentration is in the form of one of the group consisting of spins/g-catalyst, spins/g-cake, mol/g-catalyst, and mol/g-cake.
3. The method for evaluating the activity of a catalyst containing carbon deposit according to claim 1 or 2, wherein the catalyst is charged into a glass tube when the radical concentration is measured by a paramagnetic resonance spectrometer, an inert gas is introduced for 60 seconds or more before the glass tube is sealed to discharge oxygen in the glass tube, and then the glass tube is sealed by sealing a substance containing no radical such as a sealing film or plasticine or by sealing the glass tube at a high temperature by using an alcohol burner, but the catalyst temperature at the bottom of the glass tube is not higher than 70 ℃ when the catalyst is sealed at a high temperature.
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| CN201810308831.3A CN108509763B (en) | 2018-04-09 | 2018-04-09 | Method for evaluating activity of carbon deposition catalyst |
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| CN201810308831.3A CN108509763B (en) | 2018-04-09 | 2018-04-09 | Method for evaluating activity of carbon deposition catalyst |
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| CN108509763B true CN108509763B (en) | 2021-10-15 |
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| CN1280195C (en) * | 2003-12-31 | 2006-10-18 | 大连海事大学 | Method of synthesizing ammonia and fuel oil using methane and nitrogen gas |
| US10640720B2 (en) * | 2014-04-04 | 2020-05-05 | The Trustees Of Princeton University | Process for generating cool flame and flameless fuel oxidation using non-equilibrium plasma activation |
| CN105037065B (en) * | 2015-08-07 | 2016-11-23 | 北京华福工程有限公司 | A kind of acetylene hydrogenation prepares liquid phase solvent and the application thereof of ethylene slurry bed system |
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