CN108509763A - A kind of active method of evaluation carbon deposited catalyst - Google Patents
A kind of active method of evaluation carbon deposited catalyst Download PDFInfo
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- CN108509763A CN108509763A CN201810308831.3A CN201810308831A CN108509763A CN 108509763 A CN108509763 A CN 108509763A CN 201810308831 A CN201810308831 A CN 201810308831A CN 108509763 A CN108509763 A CN 108509763A
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- G—PHYSICS
- G16—INFORMATION AND COMMUNICATION TECHNOLOGY [ICT] SPECIALLY ADAPTED FOR SPECIFIC APPLICATION FIELDS
- G16C—COMPUTATIONAL CHEMISTRY; CHEMOINFORMATICS; COMPUTATIONAL MATERIALS SCIENCE
- 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 kind of methods of evaluation catalyst activity.Catalyzer coke content is one of the parameter for evaluating catalyst activity, and the mode that catalyzer coke content generally use leads to oxygen burning is measured, structure and performance not only complicated for operation but also that can lead to partial destruction catalyst because of combustion heat release.Contain the measurable free radical of paramagnetic resonance, and number of free radical relationship proportional to catalyzer coke content based on carbon deposit, thus by measure number of free radical on catalyst can estimated catalyst coke content, and then evaluate the activity of catalyst.The method have the characteristics that it is simple and easy to do, do not change catalyst structure and performance.The present invention is suitable for evaluating the activity of various carbon deposited catalysts.
Description
Technical field
The present invention relates to a kind of methods of catalyst activity evaluation, especially catalyst activity change caused by carbon deposit
Evaluation method.
Background technology
The activity of the catalyst used during oil-refining chemical can be gradually reduced, and partly cause is raw material in catalyst surface
Carbon deposit caused by reaction, the carbon deposit do not dissolve in many solvents, such as toluene, chlorobenzene, carbon disulfide, tetrahydrofuran generally.Carbon deposit
Process is related to the polycondensation reaction of free radical, and part unpaired electron can be restrained or be embedded in carbon deposit, forms EPR spectrometer
(ESR) measurable stabilized radical.Studies have shown that on ESR is measured within the scope of certain carbon deposit number of free radical and catalyst
Coke content present proportionate relationship.
Include industrially comparing the conversion ratio of raw material under fixed air speed or reaching same conversion to the evaluation of catalyst activity
Temperature needed for rate.In catalytic reaction process, the decline of catalyst activity is increased along with coke content, therefore industrial common
A parameter of the catalyzer coke content as evaluation catalyst activity.Coke content measurement generally using logical oxygen burn by the way of into
Row can obtain the coke content of catalyst according to the quality of post combustion carbon dioxide or the front and back catalyst quality difference of burning.
Invention content
Since catalyzer coke content is the parameter of characterization catalyst activity, and between catalyzer coke content and number of free radical
There is proportionate relationship again, the present invention provides a kind of evaluation carbon deposited catalysts, and active short-cut method, this method to be commented to pass through direct
The variation of number of free radical in carbon deposited catalyst is measured to evaluate catalyst activity.
The technical scheme is that：The number of free radical for measuring fresh catalyst and complete deactivation catalyst respectively, makees
For two limiting values of catalyst activity, the number of free radical of carbon deposited catalyst to be measured is compared with it, and according to formula 1
Carry out carbon deposited catalyst activity rating.
Wherein：AcFor catalyst activity parameter；
NcFor carbon deposited catalyst number of free radical；
N0For fresh catalyst number of free radical；
NdFor the number of free radical of complete deactivation catalyst.
Two parameters of g values and line width can also be obtained during determining free radicals, the two parameters can be used for studying urging
The structural information of carbon deposit in agent.
Catalyst described in above scheme can be any type of carbon deposited catalyst, but carbon deposit forming process is required to relate to
And radical reaction, contain free radical in carbon deposit.
This method has the advantages that easy to operate, activity rating accuracy is high while not destroying catalyst structure again.
Specific implementation mode
The present invention is further described with reference to embodiments, but should not be limited the scope of the invention with this.
[embodiment 1]
By the industrial residue fixed-bed hydrogenation catalyst NiMo/ γ-Al of different run times2O310 milligrams of loading internal diameters
It is 3 millimeters, in the glass tube that length is 35 millimeters, purges glass tube 60 seconds with nitrogen, to exclude oxygen in glass tube, so
After seal.Glass tube after sealing is put into paramagnetic pipe, and the number of free radical of carbon deposited catalyst is measured using EPR spectrometer.Together
When, by the fresh catalyst NiMo/ γ-Al after vulcanization2O3With the catalyst n iMo/ γ-Al of complete deactivation2O3(coke content is
18.7%) Free Radical Concentration Determination is carried out according to above method respectively.Catalyst activity (being shown with average bed thermometer), carbon deposit
Amount and number of free radical are as shown in table 1.As seen from table, as the reaction time increases, residual oil hydrocatalyst bed temperature is gradual
It increases, coke content gradually increases, and number of free radical gradually increases.
[embodiment 2]
By the industrial coal hydrogenation of tar catalyst n iMoP/ γ-Al of different run times2O3It is 3 that 10 milligrams, which are packed into internal diameter,
Millimeter, in the glass tube that length is 35 millimeters, purge glass tube 60 seconds with nitrogen, oxygen in glass tube is discharged, then
Sealing.Glass tube after sealing is put into paramagnetic pipe, and the number of free radical of carbon deposited catalyst is measured using EPR spectrometer.Together
When, by the fresh catalyst NiMoP/ γ-Al after vulcanization2O3With the catalyst n iMoP/ γ-Al of complete deactivation2O3(coke content is
15.6%) Free Radical Concentration Determination is carried out according to above method respectively.Catalyst activity (being shown with average bed thermometer), carbon deposit
Amount and number of free radical are as shown in table 2.As seen from table, as the reaction time increases, coal tar hydrogenation catalyst bed temperature by
Edge up height, and coke content gradually increases, and number of free radical gradually increases.
[embodiment 3]
By the industrial diesel hydrogenation catalyst NiMoW/ γ-Al of different run times2O3It is 3 millis that 10 milligrams, which are packed into internal diameter,
Meter, in the glass tube that length is 35 millimeters, purges glass tube 60 seconds with nitrogen, to exclude oxygen in glass tube, then seal
Mouthful.Glass tube after sealing is put into paramagnetic pipe, and the number of free radical of carbon deposited catalyst is measured using EPR spectrometer.Meanwhile
By the fresh catalyst NiMoW/ γ-Al after vulcanization2O3With the catalyst n iMoW/ γ-Al of complete deactivation2O3(coke content is
9.4%) Free Radical Concentration Determination is carried out according to above method respectively.Catalyst activity (being shown with average bed thermometer), carbon deposit
Amount and number of free radical are as shown in table 3.As seen from table, as the reaction time increases, diesel oil hydrogenation reaction bed temperature is gradual
It increases, coke content gradually increases, and number of free radical gradually increases.
Activity change in 1 residual oil hydrocatalyst reaction process of table
Activity change in 2 coal tar hydrogenation catalyst reaction process of table
Activity change during 3 diesel oil hydrogenation catalyst reaction of table
Claims (5)
1. a kind of method of catalyst activity of the evaluation containing carbon deposit.Catalyzer coke content is the important ginseng for evaluating catalyst activity
Number, and there are proportionate relationship between the free base unit weight being stabilized in catalyzer coke content and carbon deposit, therefore the feature of the present invention
It is：Catalyst activity is evaluated by measuring the number of free radical in catalyst.
2. experimental method as described in claim 1, it is characterised in that can both be used in the catalyst activity evaluation method
Number of free radical of catalyst itself be used as activity rating parameter, can also use using number of free radical as the formula of parameter as
Activity rating parameter.
3. experimental method as claimed in claim 2, it is characterised in that the activity rating formula include but are not limited to
Lower formula：Wherein：AcFor catalyst activity parameter；NcFor carbon deposited catalyst number of free radical；
N0For fresh catalyst number of free radical；NdFor the number of free radical of complete deactivation catalyst.
4. experimental method as claimed in claim 3, it is characterised in that number of free radical unit includes but are not limited to following several
Kind：Spins/g-catalyst, spins/g-coke, mol/g-catalyst, mol/g-coke.
5. the experimental method as described in claim 1-4, it is characterised in that carry out Free Radical Concentration Determination using EPR spectrometer
When, catalyst is packed into glass tube, needs to be passed through 60 seconds or more inert gases before glass channel closure, oxygen in glass tube is discharged
Gas, then to glass channel closure, the substance that sealed membrane or plasticine etc. are free of free radical had both may be used in mouth-sealing method, can also
High temperature sealing is carried out using alcohol blast burner, but glass bottom of the tube catalyst temperature is not higher than 70 DEG C when high temperature sealing.
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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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| CN108509763A true CN108509763A (en) | 2018-09-07 |
| CN108509763B CN108509763B (en) | 2021-10-15 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111579759A (en) * | 2020-05-24 | 2020-08-25 | 北京化工大学 | Method for evaluating thermal cracking starting temperature of heavy oil product |
Citations (4)
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| CN1590297A (en) * | 2003-12-31 | 2005-03-09 | 大连海事大学 | Method of synthesizing ammonia and fuel oil using methane and nitrogen gas |
| CN105037065A (en) * | 2015-08-07 | 2015-11-11 | 北京神雾环境能源科技集团股份有限公司 | Liquid-phase solvent for preparing ethylene slurry bed through acetylene hydrogenation and application thereof |
| US20170015921A1 (en) * | 2014-04-04 | 2017-01-19 | The Trustees Of Princeton University | Process for generating cool frame and flameless fuel oxidation using non-equilibrium plasma activation |
| CN107777702A (en) * | 2017-11-09 | 2018-03-09 | 常州大学 | A kind of preparation method of multi-stage porous hetero atom aluminium phosphate molecular sieve for oxidation sweetening |
-
2018
- 2018-04-09 CN CN201810308831.3A patent/CN108509763B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1590297A (en) * | 2003-12-31 | 2005-03-09 | 大连海事大学 | Method of synthesizing ammonia and fuel oil using methane and nitrogen gas |
| US20170015921A1 (en) * | 2014-04-04 | 2017-01-19 | The Trustees Of Princeton University | Process for generating cool frame and flameless fuel oxidation using non-equilibrium plasma activation |
| CN105037065A (en) * | 2015-08-07 | 2015-11-11 | 北京神雾环境能源科技集团股份有限公司 | Liquid-phase solvent for preparing ethylene slurry bed through acetylene hydrogenation and application thereof |
| CN107777702A (en) * | 2017-11-09 | 2018-03-09 | 常州大学 | A kind of preparation method of multi-stage porous hetero atom aluminium phosphate molecular sieve for oxidation sweetening |
Non-Patent Citations (1)
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| 闫玉新: "渣油催化加氢过程中催化剂表面的积炭行为研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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|---|---|---|---|---|
| CN111579759A (en) * | 2020-05-24 | 2020-08-25 | 北京化工大学 | Method for evaluating thermal cracking starting temperature of heavy oil product |
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