CN105738148A - Solid catalyst on-line sampling method - Google Patents
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- CN105738148A CN105738148A CN201410743317.4A CN201410743317A CN105738148A CN 105738148 A CN105738148 A CN 105738148A CN 201410743317 A CN201410743317 A CN 201410743317A CN 105738148 A CN105738148 A CN 105738148A
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Abstract
The invention relates to a solid catalyst on-line sampling method. The method comprises 1, filling a catalyst evaluation device with a catalyst to be evaluated, 2, starting the catalyst evaluation device so that the catalyst to be detected in a prefabricated sample pipe fully contacts with a material, and 3, in operation, separating a reactor with the catalyst to be detected from the evaluation system, dismounting the prefabricated sample pipe, taking out the catalyst to be detected and carrying out on-line sampling analysis. The method can realize on-line sampling of a catalyst in a reactor at a specific bed layer position at a moment of an evaluation process, momentarily understands a catalyst state, does not influence an evaluation process in sampling and realizes re-filling with the catalyst subjected to sampling and analysis thereby realizing multitime evaluation.
Description
Technical field
The present invention relates to a kind of solid catalyst on-line period method, belong to evaluating catalyst technical field.
Background technology
The evaluating catalyst of current oil refining process (such as hydrofinishing, hydrogenation cracking and residual hydrogenation etc.) is to be contained in fixed bed reactors by solid catalyst, carries out the operating for up to several thousand hours under certain pressure and temperature.In operation process, catalyst can be polluted by heavy metal, sulfur, nitrogen and carbon deposits etc., and catalysqt deactivation occurs, and the pore structure of catalyst and surface characteristic also can change.If the sample of catalyst can be taken out from the predetermined bed of operating reactor, so that it may relatively accurately to understand the situation of catalyst, level of deactivation and deactivation cause when not affecting unit normal run.
In commercial production is applied, generally on the diameter large-scale reactor up to several meters, online sampler is installed to take out catalyst sample, such as US Patent No. 3348419, US3442138, US3487695, US3786682, US3973440, US3653265.But for the catalyst newly researched and developed, it is necessary to first carry out the investigation of index of correlation before production application in catalyst test apparatus.Owing in catalyst test apparatus, reactor size is only small, general diameter only has tens millimeters, so there is no redundant space to install routine sampling device；On the other hand, owing to the catalyst granules of overwhelming majority catalyst granules to be evaluated and commercial Application does not have significant change in apparent size, therefore do not possess condition microminiaturized for on-line sampling device yet.
At present in evaluating catalyst, it is common that open reactor taking-up (drawing off) all catalyst after evaluating apparatus is stopped work completely and detect.But take out from outlet due to unified, it is impossible to determine various catalyst particular location in bed, therefore the catalyst to be evaluated of specific bed position cannot be monitored in real time in evaluation procedure.
The on-line period analytical equipment of the compositions such as CN2268259A provides a set of by probe tube, controls valve, cyclone separator, carries out disposable on-line period, obtains gas, liquid, catalyst sample simultaneously petrochemical production device.Owing to being fixing stiff equipped with the probe tube of probe, the catalyst sample of a point in reactor can only be obtained, so it is only applicable in the reactors such as the catalyst fluid bed such as catalytic cracking being in flow regime carries out on-line period, it is not suitable for the relatively-stationary fixed bed reactors of catalyst.Control valve is adopted to be generally needle valve additionally, due to this on-line period analytical equipment, the operation pressure (about 10MPa) of the fixed bed reactors of hydrofinishing, hydrogenation cracking and residual hydrogenation is higher than fluidized-bed reactors operation pressure (about 0.2MPa) such as catalytic cracking, the throttling space making control valve is only small, easily make catalyst blockage control valve runner, cause that this on-line period device cannot use.
CN102266742A is that a kind of Multi-channel differential reaction unit can realize the Fast Evaluation to a kind of catalyst, it is also possible to completes under identical conditions simultaneously to the evaluation of multiple catalysts and screening, is greatly improved the efficiency of evaluating catalyst.But its automatic sampling system can only analyze gas-liquid two-phase product by on-line period, and the solid catalyst sample in its reactor must take out after experiment terminates, and can not take out in real time online.Additionally its numerous reactors are all parallel relationship, it does not have series relationship, it is impossible to the simulation catalyst situation in reactor difference bed position.
Summary of the invention
In order to solve above-mentioned technical problem, the present invention provides a kind of solid catalyst sampling method, it is achieved that solid catalyst on-line period is evaluated, and the catalyst after sampling evaluation simultaneously can also recharge, it is achieved repeatedly evaluates.
To achieve these goals, the present invention adopts the following technical scheme that
A kind of solid catalyst on-line period method, comprises the steps:
1) by Catalyst packing to be evaluated in catalyst test apparatus；
2) go into operation operation, makes the catalyst to be measured in prefabricated coupon be fully contacted with material；
3) in running, will be equipped with the reactor of catalyst to be measured and depart from evaluation operation system, dismantle prefabricated coupon, take out wherein catalyst to be measured and carry out on-line period analysis；
In the present invention, described catalyst test apparatus includes multiple reactor group being connected in series, and each reactor group composes in parallel by A side and two, B side reactor, and each reactor is imported and exported and is equipped with switch valve.In evaluating running, material enters from the first reactor group of described catalyst test apparatus, flows out along pipeline from last reactor group.
Described reactor group number is 2-10；Preferred 3-5.
Each inside reactor is provided with 1-6 fixing bed bed, and the wall of reactor corresponding to each fixing bed bed is provided with the interface being arranged symmetrically with, and installs dismountable prefabricated coupon at each seam.
Described prefabricated coupon is made up of A, B two sections, and wherein A section is inserted on inside reactor bed by interface, so that the catalyst in the prefabricated coupon of A section and catalyst in reactor are fully contacted with fluid under the same conditions, makes evaluating catalyst more objective.The A section surface going deep into inside reactor is provided with multiple aperture, bore dia 0.5-4mm, the preferred 40-60% of percent opening, and the gas-liquid two-phase both ensured in reactor passes freely through, and makes again catalyst and material be fully contacted；Described B section inert agents is filled, it is preferable that quartz sand, and B section is connected with reactor sealing joint, it is preferable that thread seal connects, to ensure that in reactor, medium is not revealed.Additionally, be additionally provided with atmospheric valve on each reactor and purge displacement valve.
All reactor groups can install temperature control in same heating furnace concentratedly, it is possible to is respectively provided with the independent temperature control of heating furnace.
As the preferred embodiment of the present invention, described solid catalyst on-line period method specifically includes following steps:
Described step 1), the catalyst to be evaluated of variety classes and consumption is seated in corresponding reactor group A side and two, B side reactor according to technological requirement；Wherein in same reactor group, in A, B side reaction device, catalyst filling mode is identical, and by each prefabricated probe tube on reactor built with the identical catalyst to be measured of corresponding bed；
Described step 2), before going into operation, all reactors are imported and exported switch valve and all opens, making each reactor group is series relationship, and in same reactor group, A, B side reaction device is parallel relationship；Now in two reactors of same reactor group, each technological parameter is all identical；
Catalyst test apparatus is carried out airtight, starts after qualified catalyst is evaluated.
Described step 3), first simultaneously close off the import and export switch valve of A side reaction device in each reactor group so that it is depart from and evaluate operation system；And inlet amount is reduced half, it is ensured that in all B side reaction devices, technological parameter is constant；Now, material will carry out in the B side reaction device of each reactor group；
After the cooling of catalyst place to be measured reactor, emptying and inert gas purge, prefabricated coupon on it is dismantled, takes out wherein catalyst and carry out phenetic analysis；
Take out the prefabricated coupon of catalyst to be measured and can fill identical catalyst or implant reinstalls on reactor, after sealed, A side reaction device is re-started intensification, assigned temperature to be achieved and stable after, open all reactor import and export switch valves in A side and again switch back in evaluation operation system, recover the state before sampling,, again evaluate.Properly functioning without influence on evaluating apparatus in the process.
As the present invention another preferred embodiment, described solid catalyst adopt with one for a mode on-line period, specifically include following steps:
Described step 1), the catalyst to be evaluated of variety classes and consumption is seated in corresponding reactor group A side and two, B side reactor according to technological requirement；Wherein in same reactor group, in A, B side reaction device, catalyst filling mode is identical, and by each prefabricated probe tube on reactor built with the identical catalyst to be measured of corresponding bed；
Described step 2), before going into operation, the import and export switch valve of all reactors all to be opened, it is achieved each reactor group is series relationship, in same reactor group, A, B side reaction device is parallel relationship；
Evaluating apparatus is carried out airtight；After airtight detection is qualified, being opened by the import and export switch valve of all A side reaction devices, and closed by the import and export switch valve of all B side reaction devices, in each reactor group, reactor realizes " with one for one；
Catalyst test apparatus goes into operation and catalyst is evaluated, and all reactors is heated up simultaneously.
Described step 3), the switch valve that a certain for B side reactor is imported and exported is opened, simultaneously closes off A side and import and export switch valve with the reactor that group is corresponding, make material enter in B side reaction device, now B side reaction device adds in evaluation system；In the constant situations of system process parameters such as temperature, pressure and flow, make a certain reactor in A side become standby reactor, depart from evaluation system and be sampled operation, and corresponding standby B side reaction device becomes with in reactor addition evaluation system；
The A side reaction device equipped with catalyst to be measured isolated is lowered the temperature, emptying and inert gas purge, dismantle prefabricated coupon, take out wherein catalyst samples and carry out phenetic analysis.
Take out the prefabricated coupon of catalyst to be measured and can fill identical catalyst or implant reinstalls on reactor, after airtight, A side reaction is thought highly of new intensification, assigned temperature to be achieved and stable after, open A side reaction device and import and export switch valve, simultaneously closing off B side reaction device and import and export switch valve, make A side reaction think highly of and be newly incorporated in the pipe-line system of evaluating apparatus, B side reaction thinks highly of new isolation, recover the state before sampling, again evaluate.Properly functioning without influence on evaluating apparatus in the process.
Compared with prior art, solid catalyst on-line period method of the present invention is adopted, it is possible to achieve at certain time point of evaluation procedure and on specific bed position, the catalyst in reactor is carried out on-line period, understand the situation of each catalyst at any time；In sampling process, whole evaluation procedure is stable, not by sampling effect；Catalyst after sample analysis can also recharge simultaneously, it is achieved repeatedly evaluates.
Accompanying drawing explanation
Fig. 1 is the embodiment of the present invention 1 solid catalyst on-line period method schematic diagram.
Fig. 2 is the embodiment of the present invention 1 or 2 structure of reactor schematic diagram.
Fig. 3 is the prefabricated coupon structural representation of the embodiment of the present invention 1 or 2.
Fig. 4 is the prefabricated coupon sectional view of the embodiment of the present invention 1 or 2.
Fig. 5 is the embodiment of the present invention 2 solid catalyst on-line period method schematic diagram.
Fig. 6 is existing catalyst test apparatus structural representation.
In figure: 1-3. reactor group；4-5. reactor；6. switching valve；7. device go into operation after the flow direction of material；8. the flow direction of material during sampling；9. reactor interface；10. prefabricated coupon；11. catalyst samples；12. atmospheric valve；13. purge displacement valve；14. solid catalyst；15. screw thread is extremely stifled；16. prefabricated coupon screw thread；17. prefabricated coupon perforate；18. reactor group.
Detailed description of the invention
Following example are used for illustrating the present invention, but are not limited to the scope of the present invention.
Embodiment 1 solid catalyst on-line period method
Residual oil is enriched the impurity (such as S, N, Ni, V etc.) of complexity, makes oil deteriorate, therefore in residual hydrogenation Catalytic processes, prolong residual oil flow direction and load protective agent, catalyst for demetalation, desulphurization catalyst and de-carbon residue catalyst respectively.The present embodiment is evaluated as example with residual oil hydrocatalyst, to gather residuum hydrodesulfurization catalyst in evaluation procedure, describes residuum hydrodesulfurization catalyst on-line period method in detail.
Described catalyst test apparatus as in Figure 2-4, including four tandem reactor group 1-3,18；Each described reactor group composes in parallel by A side and two, B side reactor; as the 3rd reactor group 3 is composed in parallel by A side reaction device 4 and B side reaction device 5; wherein; protective agent is loaded in the first reactor group 1 and prefabricated coupon 10; filling catalyst for demetalation in second reactor group 2 and prefabricated coupon 10; filling desulphurization catalyst in 3rd reactor group and prefabricated coupon, the 4th reactor group and the de-carbon residue catalyst of filling in prefabricated coupon 10；Each reactor is additionally provided with import and export switch valve 6.
In evaluating catalyst running, residual oil enters from the first reactor group 1, flows through the second reactor group the 2, the 3rd reactor group 3, flows out from the 4th reactor group 18.
Wherein, being provided with 3 beds at each inside reactor, wall of reactor corresponding to each bed position is provided with 2 interfaces being arranged symmetrically with 9, and installs dismountable prefabricated coupon 10 at each seam；
As shown in Figure 4, described prefabricated coupon is made up of A, B two sections, and wherein A section is inserted on inside reactor bed, so that the catalyst in prefabricated coupon A section and catalyst in reactor are fully contacted with fluid under the same conditions, makes evaluating catalyst more objective.
The A section surface going deep into inside reactor is provided with multiple aperture 17, bore dia 1-2mm, percent opening 50%, and the gas-liquid two-phase both ensured in reactor passes freely through, and makes again catalyst and material be fully contacted；
Described B section quartz sand is filled, and B section pipe appearance is helicitic texture 16, is connected with thread seal with reactor interface, and uses extremely stifled 15 sealings of screw thread, to ensure that in reactor, medium is not revealed.Additionally, be additionally provided with atmospheric valve 12 on each reactor and purge displacement valve 13.
All reactor groups can install temperature control in same heating furnace concentratedly, it is possible to is respectively provided with the independent temperature control of heating furnace.
On-line period method in described desulphurization catalyst evaluation procedure, as it is shown in figure 1, comprise the steps:
1) by the protective agent Catalyst packing two reactors in the first reactor group; catalyst for demetalation is loaded in two reactors in the second reactor group; desulphurization catalyst is loaded in two reactors in the 3rd reactor group, by two reactors in de-carbon residue Catalyst packing to the 4th reactor group；Wherein in same reactor group, in A, B side reaction device, catalyst filling mode is identical, and loads, by each prefabricated probe tube on reactor, the catalyst to be measured that corresponding bed is identical；
2) all being opened by the import and export switch valve 6 of reactor before going into operation, it is achieved each reactor group is series relationship, in same reactor group, A, B side reaction device is parallel relationship；Evaluating apparatus is carried out airtight, airtight qualified after, start catalyst is carried out activity rating.Appreciation condition is: reaction temperature 385 DEG C, hydrogen dividing potential drop 14.7MPa, air speed 0.24h-1, hydrogen to oil volume ratio 700:1；
After evaluating apparatus goes into operation, in flow direction of material such as Fig. 1 shown in dotted line 7, in two reactors of same reactor group, each technological parameter is all identical；
3), after running 200 hours, the desulphurization catalyst of the A side reaction device 4 of the 3rd reactor group is carried out on-line period；Concrete grammar:
First the import and export switch valve 6 of A side reaction device in all reactor groups is all closed so that it is depart from the system of operation simultaneously；And resid feed amount is decreased to original half, now in each reactor group, in B side reaction device, process conditions are all constant, and residual oil evaluation in B side reaction device is normally carried out；
The reactor 4 equipped with desulphurization catalyst isolated is lowered the temperature, emptying and inert gas purge, the prefabricated coupon 10 corresponding from the specific bed of reactor 4 takes off one, takes out wherein catalyst samples and carries out phenetic analysis；
In the prefabricated sampler disassembled, load identical catalyst reinstall back on reactor 4, after airtight, reactor 4 is heated up again, all A side reaction device terminal valves 6 are opened after assigned temperature to be achieved, resid feed amount is recovered to normal discharge simultaneously, make all A side reactions think highly of newly to be incorporated in the pipe-line system of evaluating apparatus and recover the state before sampling, and accumulative timing, thus completing the purpose of desulphurization catalyst on-line period.When plant running 400 is little during sampling, can operation when reactor 5 reaction repeated device 4 samples, when plant running to 600 is little constantly, then take the prefabricated coupon 10 of other bed of reactor 4, so repeatedly, it may be achieved the on-line period of device evaluation procedure random time.
Desulphurization catalyst on-line period analyzes result in Table 1.
Different time sections catalyst analysis result in table 1 desulphurization catalyst evaluation procedure
| Evaluation time, hour | C, % | H, % | Ni, ppm | V, ppm |
| 200 | 7.34 | 1.14 | 423 | 325 |
| 400 | 9.73 | 1.06 | 663 | 405 |
| 600 | 10.67 | 1.04 | 721 | 614 |
| 800 | 10.73 | 1.05 | 842 | 728 |
| 1000 | 10.95 | 1.06 | 1005 | 917 |
As shown in Table 1, method of the present invention is adopted to can be implemented in certain time point of evaluation procedure and on specific bed position, the catalyst in reactor carried out on-line period；In sampling process, whole evaluation procedure is stable, not by sampling effect.
Embodiment 2 adopts " with one for one " mode to solid catalyst on-line period
Residual oil is enriched the impurity (such as S, N, Ni, V etc.) of complexity, makes oil deteriorate, therefore in residual hydrogenation Catalytic processes, prolong residual oil flow direction and load protective agent, catalyst for demetalation, desulphurization catalyst and de-carbon residue catalyst respectively.The present embodiment is evaluated as example with residual oil hydrocatalyst, to gather residuum hydrodesulfurization catalyst in evaluation procedure, describes in detail and adopts a preparation and a use formula on-line period method to be sampled desulphurization catalyst in residual hydrogenation process.
Described catalyst test apparatus as in Figure 2-4, including four tandem reactor group 1-3,18；Each described reactor group composes in parallel by A side and two, B side reactor; as the 3rd reactor group 3 is composed in parallel by A side reaction device 4 and B side reaction device 5; wherein; protective agent is loaded in the first reactor group 1 and prefabricated coupon 10; filling catalyst for demetalation in second reactor group 2 and prefabricated coupon 10; the desulphurization catalyst that in 3rd reactor group and prefabricated coupon, filling is to be evaluated, the 4th reactor group and the de-carbon residue catalyst that in prefabricated coupon 10, filling is evaluated；Each reactor is additionally provided with import and export switch valve 6.
Wherein, being provided with 3 beds at each inside reactor, wall of reactor corresponding to each bed position is provided with 2 interfaces being arranged symmetrically with 9, and installs dismountable prefabricated coupon 10 at each seam；
As shown in Figure 4, described prefabricated coupon is made up of A, B two sections, and wherein A section is inserted on inside reactor bed, so that the catalyst in prefabricated coupon A section and catalyst in reactor are fully contacted with fluid under the same conditions, makes evaluating catalyst more objective.
The A section surface going deep into inside reactor is provided with multiple aperture 17, bore dia 2mm, percent opening 52%, and the gas-liquid two-phase both ensured in reactor passes freely through, and makes again catalyst and material be fully contacted；
Described B section quartz sand is filled, and B section pipe appearance is helicitic texture 16, is connected with thread seal with reactor interface, uses extremely stifled 15 sealings of screw thread, to ensure that in reactor, medium is not revealed.Additionally, be additionally provided with atmospheric valve 12 on each reactor and purge displacement valve 13.
All reactor groups can install temperature control in same heating furnace concentratedly, it is possible to is respectively provided with the independent temperature control of heating furnace.
On-line period method in described desulphurization catalyst evaluation procedure, as it is shown in figure 5, comprise the steps:
1) by the protective agent Catalyst packing two reactors in the first reactor group; catalyst for demetalation is loaded in two reactors in the second reactor group; desulphurization catalyst is loaded in two reactors in the 3rd reactor group, by two reactors in de-carbon residue Catalyst packing to the 4th reactor group；Wherein in same reactor group, in A, B side reaction device, catalyst filling mode is identical, and loads, by each prefabricated probe tube on reactor, the catalyst to be measured that corresponding bed is identical；
2) all being opened by the import and export switch valve 6 of all reactors before going into operation, it is achieved each reactor group is series relationship, in same reactor group, A, B side reaction device is parallel relationship, carries out airtight to evaluating apparatus；Airtight qualified after, the import and export switch valve 6 of all A side reaction devices is all opened, and the import and export switch valve 6 of all B side reaction devices is all closed, in each reactor group, reactor realizes " with one for one ", starts catalyst is carried out activity rating.
Appreciation condition is: reaction temperature 385 DEG C, hydrogen dividing potential drop 14.7MPa, air speed 0.24h-1, hydrogen to oil volume ratio 700:1；
After evaluating apparatus goes into operation, A, B side reaction device of all reactor groups is heated up, in flow direction of material such as Fig. 5 shown in dotted line 7 simultaneously；
3), after running 200 hours, desulphurization catalyst in the A side reaction device 4 of the 3rd reactor group is carried out on-line period；Concrete grammar:
First being opened by the switch valve that B side reaction device 5 is imported and exported, simultaneously close off the switch valve that A side reaction device 4 is imported and exported, make material enter in B side reaction device 5, in flow direction of material such as Fig. 5 shown in solid line 8, now B side reaction device 5 adds in evaluation system.Make when not affecting the technological parameters such as the temperature of other reactors, pressure and flow A side reaction device 4 become standby reactor, depart from evaluation system, it is simple to be sampled operation, and standby B side reaction device 5 becomes, with reactor, adding in evaluation system.
The A side reaction device 4 equipped with desulphurization catalyst isolated is lowered the temperature, emptying and inert gas purge, the prefabricated coupon 10 corresponding from the specific bed of A side reaction device 4 takes off one, takes out wherein catalyst samples and is evaluated analyzing；
In the prefabricated sampler disassembled, load identical catalyst reinstall back on A side reaction device 4, after airtight, A side reaction device 4 is heated up again, A side reaction device 4 terminal valve 6 is opened after assigned temperature to be achieved, simultaneously close off the switch valve that B side reaction device 5 is imported and exported, making A side reaction device 4 again be incorporated in the pipe-line system of evaluating apparatus, B side reaction device 5 is isolated again, recovers the state before sampling, and accumulative timing, thus completing the purpose of desulphurization catalyst on-line period.When plant running 400 is little during sampling, can in reactor 4 repeated sampling；When plant running to 600 is little constantly, then take the prefabricated coupon 10 of other bed of reactor 4, so repeatedly, it may be achieved the on-line period of device evaluation procedure random time.
Desulphurization catalyst on-line period analyzes result in Table 2.
Different time sections catalyst analysis result in table 2 desulphurization catalyst evaluation procedure
| Evaluation time, hour | C, % | H, % | Ni, ppm | V, ppm |
| 200 | 7.34 | 1.14 | 423 | 325 |
| 400 | 9.75 | 1.07 | 660 | 401 |
| 600 | 10.69 | 1.04 | 718 | 599 |
| 800 | 10.81 | 1.03 | 835 | 708 |
| 1000 | 11.01 | 1.04 | 994 | 894 |
As shown in Table 2, use one of the present invention is adopted to can be implemented in certain time point of evaluation procedure for a method and on specific bed position, the catalyst in reactor carried out on-line period；In sampling process, whole evaluation procedure is stable, not by sampling effect.
Comparative example 1
For 1000 hours stability tests of residual oil hydrocatalyst, catalyst loading pattern is shown in that Fig. 6, estimation of stability condition are: reaction temperature 385 DEG C, hydrogen dividing potential drop 14.7MPa, air speed 0.24h-1, hydrogen to oil volume ratio 700:1；Catalyst is not sampling in the middle of evaluation procedure in 1000 hours, takes desulphurization catalyst and characterize after 1000 hours terminate, and result is in Table 3.
After 31000 hours stability tests of table, desulphurization catalyst analyzes result
| Evaluation time, hour | C, % | H, % | Ni, ppm | V, ppm |
| 1000 | 11.05 | 1.07 | 1009 | 921 |
Contrast table 1, table 2, table 3 are known, on-line period method of the present invention is ensureing to analyze that result is stable, under reliable premise, realize, at certain time point of evaluation procedure and on specific bed position, the catalyst in reactor is carried out on-line period, understand the situation of each beds at any time；Catalyst after sample analysis can also recharge simultaneously, it is achieved repeatedly evaluates.
Although, above the present invention is described in detail with a general description of the specific embodiments, but on basis of the present invention, it is possible to it is made some modifications or improvements, and this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to the scope of protection of present invention.
Claims (9)
1. a solid catalyst on-line period method, it is characterised in that comprise the steps:
1) by Catalyst packing to be evaluated in catalyst test apparatus；
Described catalyst test apparatus includes multiple reactor group being connected in series, and each reactor group composes in parallel by A side and two, B side reactor, and each reactor is imported and exported and is equipped with switch valve；
Each inside reactor is provided with multiple fixing bed bed；
Wall of reactor corresponding to each fixing bed bed is provided with the interface being arranged symmetrically with, and installs dismountable prefabricated coupon at each seam；
2) go into operation operation, makes the catalyst to be measured in prefabricated coupon be fully contacted with material；
3) in running, will be equipped with the reactor of catalyst to be measured and depart from evaluation operation system, dismantle prefabricated coupon, take out wherein catalyst to be measured and carry out on-line period analysis.
2. solid catalyst on-line period method according to claim 1, it is characterised in that described reactor group number is 2-10.
3. solid catalyst on-line period method according to claim 1, it is characterised in that each inside reactor is provided with 1-6 fixing bed bed.
4. solid catalyst on-line period method according to claim 1, it is characterised in that described prefabricated coupon is made up of A, B two sections, and wherein A section is inserted on inside reactor bed by interface, and its surface is provided with multiple aperture；Described B section inert agents is filled, and is connected with reactor sealing joint.
5. solid catalyst on-line period method according to claim 1, it is characterised in that all reactor groups can install temperature control in same heating furnace concentratedly, or is respectively provided with the independent temperature control of heating furnace.
6. according to the arbitrary described solid catalyst on-line period method of claim 1-5, it is characterized in that, in described step 1) in, the catalyst to be evaluated of variety classes and consumption is seated in catalyst test apparatus corresponding reactor group A side according to technological requirement and in the reactor of two, B side；Wherein in same reactor group, in A, B side reaction device, catalyst filling mode is identical, and by each prefabricated probe tube on reactor built with the identical catalyst to be measured of corresponding bed；
In described step 2) in, before going into operation, all reactors are imported and exported switch valve and all opens, making each reactor group is series relationship, and in same reactor group, A, B side reaction device is parallel relationship；Catalyst test apparatus is carried out airtight, starts after qualified catalyst is evaluated；
In described step 3) in, close the import and export switch valve of A side reaction device in each reactor group, and inlet amount is reduced half；Will be disengaged from the catalyst place to be measured reactor cooling of evaluation system, emptying and inert gas purge, dismantle prefabricated coupon, take out wherein catalyst and carry out phenetic analysis.
7. solid catalyst on-line period method according to claim 6, it is characterised in that the prefabricated coupon identical catalyst of filling or the implant of taking out catalyst to be measured reinstall on reactor, after sealed, A side reaction device are re-started intensification；After question response device reaches assigned temperature and be stable, open all reactor import and export switch valves in A side and again switch back in evaluation operation system, recover the state before sampling, again evaluate.
8. according to the arbitrary described solid catalyst on-line period method of claim 1-5, it is characterised in that
In described step 1) in, the catalyst to be evaluated of variety classes and consumption is seated in catalyst test apparatus corresponding reactor group A side according to technological requirement and in the reactor of two, B side；Wherein in same reactor group, in A, B side reaction device, catalyst filling mode is identical, and by each prefabricated probe tube on reactor built with the identical catalyst to be measured of corresponding bed；
In described step 2) in, before going into operation, the import and export switch valve of all reactors is all opened, evaluating apparatus is carried out airtight, after qualified, the import and export switch valve of all A side reaction devices is opened, and the import and export switch valve of all B side reaction devices is closed, it is achieved " with one for one；Catalyst test apparatus goes into operation and catalyst is evaluated, and all reactors is heated up simultaneously；
In described step 3) in, the switch valve that a certain for B side reactor is imported and exported is opened, simultaneously closes off A side and import and export switch valve with the reactor that group is corresponding；The A side reaction device equipped with catalyst to be measured isolated is lowered the temperature, emptying and inert gas purge, dismantle prefabricated coupon, take out wherein catalyst samples and carry out phenetic analysis.
9. solid catalyst on-line period method according to claim 8, it is characterized in that, take out the prefabricated coupon of catalyst to be measured and can fill identical catalyst or implant reinstalls on reactor, after airtight, A side reaction is thought highly of new intensification, assigned temperature to be achieved and stable after, open A side reaction device and import and export switch valve, simultaneously close off B side reaction device and import and export switch valve, recover the state before sampling, in the process properly functioning without influence on evaluating apparatus.
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| US5417846A (en) * | 1990-03-29 | 1995-05-23 | Institut Francais Du Petrole | Hydrotreatment method for a petroleum residue or heavy oil with a view to refining them and converting them to lighter fractions |
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| CN104140839A (en) * | 2014-07-25 | 2014-11-12 | 山西沸石科技有限公司 | Continuous reaction and regeneration technology used for conversion of methanol to gasoline through stationary bed adiabatic reactors |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4017382A (en) * | 1975-11-17 | 1977-04-12 | Gulf Research & Development Company | Hydrodesulfurization process with upstaged reactor zones |
| US5417846A (en) * | 1990-03-29 | 1995-05-23 | Institut Francais Du Petrole | Hydrotreatment method for a petroleum residue or heavy oil with a view to refining them and converting them to lighter fractions |
| JPH05202370A (en) * | 1991-09-26 | 1993-08-10 | Inst Fr Petrole | Method for hydrogenating heavy hydrocarbon fraction to purify it and convert it into lighter hydrocarbon fraction |
| CN1484684A (en) * | 2000-12-11 | 2004-03-24 | 法国石油公司 | Method for hydrotreatment of heavy hydrocarbon fraction with switchable reactors and reactors capable of being shorted out |
| CN102375035A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Laboratory evaluation method for alkene fluidized bed catalyst prepared from methanol |
| CN103102940A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Combined process for hydrotreatment of heavy oil |
| CN104140839A (en) * | 2014-07-25 | 2014-11-12 | 山西沸石科技有限公司 | Continuous reaction and regeneration technology used for conversion of methanol to gasoline through stationary bed adiabatic reactors |
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