CN1202211C - Use method of reduced catalyst - Google Patents
Use method of reduced catalyst Download PDFInfo
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- CN1202211C CN1202211C CN 02133143 CN02133143A CN1202211C CN 1202211 C CN1202211 C CN 1202211C CN 02133143 CN02133143 CN 02133143 CN 02133143 A CN02133143 A CN 02133143A CN 1202211 C CN1202211 C CN 1202211C
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- catalyst
- live
- activity
- catalyzer
- regenerated
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- 239000003054 catalyst Substances 0.000 title claims abstract description 215
- 238000000034 method Methods 0.000 title claims abstract description 35
- 230000000694 effects Effects 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 230000008929 regeneration Effects 0.000 claims description 16
- 238000011069 regeneration method Methods 0.000 claims description 16
- 230000001186 cumulative effect Effects 0.000 claims description 13
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 11
- 230000015556 catabolic process Effects 0.000 claims description 6
- 238000006731 degradation reaction Methods 0.000 claims description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 description 11
- 230000008569 process Effects 0.000 description 7
- 239000003921 oil Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910015338 MoNi Inorganic materials 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 101100004280 Caenorhabditis elegans best-2 gene Proteins 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a using method of a catalyst of which the performance can not satisfy original reaction after being regenerated. In the using method, mainly, a small amount of homogeneous fresh catalyst is mixed into a regenerated catalyst; then, the activity of the regenerated catalyst is evaluated. According to performance, the catalyst is respectively used, namely that the catalyst is used for an original reaction process or downgrading. The fresh catalyst and the regenerated catalyst are mutually matched in the method of the present invention. The performance of a mixed catalyst is higher than that of the addition of the fresh catalyst and the regenerated catalyst. The method of the present invention can fully use the catalysts, reduce energy consumption, expand the using range of the regenerated catalysts, economize resources and improve economic benefits.
Description
1, technical field
The present invention relates to a kind of using method of regenerated catalyst, particularly can not satisfy the using method of the regenerated catalyst of former reaction process reactivity worth.
2, background technology
The normal catalysis process that adopts as hydrocracking, hydrofining etc., is handled raw material economically and they is converted into various useful purpose products in oil refining, chemical process.Loss is active gradually in the long-term operation process for the employed catalyzer of these processes, and tracing it to its cause is owing to the deposition of carbon deposit at catalyst surface causes to a great extent.A lot of catalyzer, by the regeneration of burn off carbon deposit, activity can partially or completely be restored, and still can continue to use in industrial production.The catalyzer that the has use of can repeatedly regenerating to reach save energy, increases the purpose of benefit.Simultaneously, also can reduce the wasting of resources.
Performance recovery situation after the decaying catalyst regeneration is determining the purposes of catalyzer.In principle, by analysis to the decaying catalyst physico-chemical property, and the service condition of combined catalyst, think that activity, selectivity and the life-span etc. of catalyzer after the regeneration of the method for less expensive all can reach or during near the live catalyst level, catalyzer just tool regeneration is worth.Quite serious when the inactivation of estimated catalyst, when the every performance distance live catalyst of the regenerated catalyst that obtains differs big, can abandon regeneration to decaying catalyst.But; in fact through regular meeting following situation takes place: the good catalyzer of performance after some is thought and regenerates; because regeneration condition is not ideal; perhaps the actual reproduction result has a certain distance with the preceding hope of regenerating, and the regenerated catalyst that the result obtains can not satisfy the industrial minimum standard that requires performance fully.If will continue to use, face great risk, but will cause certain waste again as waste treatment, how to handle the problem that these catalyzer are exist actuallies.In fact, itself just there is this problem in the process of argumentation before some decaying catalyst regeneration.Because the scope that this class problem relates to is bigger, so economic benefit and social benefit are considerable.Patent USP4,888,316 suggestions, to useless Hydrobon catalyst through treating processes such as grind, add aluminum oxide, moulding and make charcoal, the catalyzer that can reuse with preparation, but this method exists performance difficulty and active insufficient problem.
If can carry out modulation to the regenerated catalyst that reactivity worth can not satisfy former reaction process, make its reactive behavior reach needed standard, will be easy to address the above problem.Find after deliberation, add a small amount of live catalyst of the same type in the catalyzer after regeneration, its combined reaction performance far above both simply add and, therefore in such regenerated catalyst, sneak into a certain amount of similar live catalyst and be and a kind ofly select preferably.Present catalyst regeneration process almost all adopts device to regenerate outward, sneaks into a certain amount of similar live catalyst to improve catalyst activity in reactivity worth can not satisfy the regenerated catalyst of former reaction process, is easy to technically implement.
3, summary of the invention
At the deficiencies in the prior art, the invention provides a kind of effectively compensation regeneration catalyst reaction performance, expansion regenerated catalyst use range is with the method that economizes on resources, increases the benefit.
The inventive method detailed process is as follows:
Compare the live catalyst activity be more than 75%, be preferably sneak into 1%～50% in the regenerated catalyst more than 80%, the similar live catalyst of best 2%～30% (accounting for the catalyzer cumulative volume), carry out activity rating then, looking evaluation effect selects the use of this regenerated catalyst, promptly when the performance of mixed catalyst reaches requiring of former reaction, be used for former reaction process, when the performance of mixed catalyst is lower than requiring of former reaction, other reaction process that is used to suit.Other suitable reaction process refers to the reaction process that reaction conditions is gentle, required catalyst performance is low slightly.
For hydrocracking catalyst, general requirement regenerated catalyst activity must reach more than 90% of live catalyst, can be used for former reaction process.To activity only is the regenerated catalyst of live catalyst 85-90%, if sneak into 2-15%, is preferably the live catalyst of 5-10%, and this regenerated catalyst can be used for former reaction process.Can to activity only be the regenerated catalyst of live catalyst 80-85%, reuse to have query, if sneak into 10-50%, is preferably the live catalyst of 20-30%, and this regenerated catalyst is used for former reaction process.
For Hydrobon catalyst, general requirement regenerated catalyst activity must reach more than 93% of live catalyst, can be used for former reaction process.To activity only is the regenerated catalyst of live catalyst 90-93%, can use this degradation, if sneak into 1-10%, is preferably the live catalyst of 3-7%, and this regenerated catalyst can be used for former reaction process.To activity only is the regenerated catalyst of live catalyst 85-90%, can reuse and have query, if sneak into 5-15%, be preferably the live catalyst of 8-12%, the use of can demoting of this regenerated catalyst, if sneak into 15-50%, be preferably the live catalyst of 20-30%, this regenerated catalyst is used for former reaction process.Above-mentioned degradation is meant that reducing it uses severity, the metal equal size in processing raw material as reduction or as make-up catalyst.We are modal, originally are used for the catalyzer of VGO hydrotreatment, are used as catalyst for hydrogenation of fraction oil, also can be used as at last to handle petroleum naphtha or used as the catalyzer of an anti-or guard reactor.When processing siliceous stock oil, can be seated in an anti-top to save raw catalyst.After reactor catalyst is cast aside head, also can adopt the catalyzer catalyzer as a supplement after the regeneration.
The inventive method can promote the use properties of catalyzer so greatly by add a small amount of live catalyst of the same type in regenerated catalyst, the raising of performance considerably beyond both performances simply add and, therefore can make regenerated catalyst obtain to make full use of.Simultaneously, because the live catalyst that adds is less, be rational economically therefore.Simple, the easy to implement operation of the inventive method.Initial activity was higher when the inventive method had also overcome the live catalyst use, and the problem of carbon deposit makes catalyst performance obtain stable performance easily.
4, embodiment
The inventive method adopts the method for sneaking into a certain amount of similar live catalyst in regenerated catalyst, to improve the regenerated catalyst activity, particularly can not satisfy the regenerated catalyst of former reaction process to reactivity worth.
The regenerated catalyst that the present invention relates to comprises that all regeneration effects are slightly poor, but still the catalyzer of the certain use value of tool, especially hydrogenation catalyst, as Hydrobon catalyst, hydrocracking catalyst etc.Such catalyzer generally is to comprise the metal of VIB, VIIB, VIII family, or gauge in the bimetal of this scope or many metallic salts be supported on aluminum oxide or (with) other is prepared from as carriers such as silicon oxide, pure aluminium silicate, zeolites.The shape of catalyzer generally is cylindrical, spherical or leafy shape, and diameter is the 0.5-3.5 millimeter, and length is the 1.5-10.0 millimeter.
In the present invention, the live catalyst content of sneaking in the regenerated catalyst is lower than 30% and is advisable for being lower than 50%, being preferably.Though it is big that the shared ratio of live catalyst heals, the reactivity worth that regenerated catalyst shows is good more, and economical efficiency is considered in above-mentioned selection, also is simultaneously the conclusion that draws on this catalyzer of eliminating is regenerated the basis once more.
In the present invention, live catalyst preferably evenly is blended in the regenerated catalyst, and the catalyst ratio by volume is calculated.
Be described in further detail method of the present invention below by embodiment.
Embodiment 1
A kind of regenerated MoNi/Al
2O
3Hydrobon catalyst, the activity change of sneaking into its live catalyst (3936 Hydrobon catalysts that Fushun petrochemical corporation (complex) catalyst plant is produced) front and back sees Table one.
Embodiment 2
A kind of regenerated WMoNi/Al
2O
3Hydrobon catalyst, the activity change of sneaking into its live catalyst (the FH-5 Hydrobon catalyst that Hua Hua group company in Wenzhou produces) front and back sees Table one.
The catalyst activity changing conditions that table one relates to
| Embodiment 1 | Relative reactivity, % | Embodiment 2 | Relative reactivity, % |
| Regenerated catalyst | 88 | Regenerated catalyst | 91 |
| 97v% regenerated catalyst+3v% live catalyst | 88 | 97v% regenerated catalyst+3v% live catalyst | 93 |
| 90v% regenerated catalyst+10v% live catalyst | 92 | 90v% regenerated catalyst+10v% live catalyst | 95 |
| 75v% regenerated catalyst+25v% live catalyst | 94 | 75v% regenerated catalyst+25v% live catalyst | 95 |
| 60v% regenerated catalyst+40v% live catalyst | 96 | 60v% regenerated catalyst+40v% live catalyst | 97 |
| Live catalyst | 100 | Live catalyst | 100 |
*The relative reactivity of catalyzer is estimated on anti-little, stablizes sampling analysis after 12 hours.Main operational condition is catalyst levels: 10ml; Stock oil: 2160ppm thiophene/lam-oil; Volume space velocity: 1.8h
-1Reaction pressure: 4.0MPa; Hydrogen flow rate: 120ml/min.
As can be seen from Table I, under identical activity rating condition, sneak into similar live catalyst and improved the regenerated catalyst activity greatly.To activity is the regenerated catalyst of live catalyst 88% only, sneaks into 3% live catalyst, and effect is also not obvious; After sneaking into 10%, catalyst activity reaches 92%, the use of can demoting; Mixed volume is 25% and 40% o'clock, and this regenerated catalyst is used for former reaction process.To activity is the regenerated catalyst of live catalyst 91%, can use this degradation; If sneak into 3%, behind the l0%, 25% and 40% live catalyst, catalyst activity can reach more than 93% respectively, can be used for former reaction process.
Embodiment 3
A kind of regenerated WNi/USY+Al
2O
3Hydrocracking catalyst, the activity change of sneaking into its live catalyst (3905 hydrocracking catalysts that Fushun petrochemical industry catalyst plant is produced) front and back sees Table two.
Embodiment 4
A kind of regenerated MoNi/USY+Al
2O
3Hydrocracking catalyst, the activity change of sneaking into its live catalyst (3824 hydrocracking catalysts that Fushun petrochemical industry catalyst plant is produced) front and back sees Table two.
The catalyst activity changing conditions that table two relates to
| Embodiment 3 | Relative reactivity, % | Embodiment 4 | Relative reactivity, % |
| Regenerated catalyst | 83 | Regenerated catalyst | 87 |
| 97v% regenerated catalyst+3v% live catalyst | 85 | 97v% regenerated catalyst+3v% live catalyst | 90 |
| 90v% regenerated catalyst+8v% live catalyst | 89 | 92v% regenerated catalyst+8v% live catalyst | 93 |
| 85v% regenerated catalyst+15v% live catalyst | 92 | 85v% regenerated catalyst+15v% live catalyst | 94 |
| 60v% regenerated catalyst+40v% live catalyst | 93 | - | - |
| Live catalyst | 100 | Live catalyst | 100 |
*The relative reactivity of catalyzer is estimated on anti-little, stablizes sampling analysis after 12 hours.Main operational condition is catalyst levels: 10ml; Stock oil: octane; Volume space velocity: 1.0h
-1Reaction pressure: 6.5Mpa; Hydrogen flow rate: 120ml/min.
As can be seen from Table II, under identical activity rating condition, sneak into similar live catalyst and improved the regenerated catalyst activity greatly.To activity is the regenerated catalyst of live catalyst 83% only, sneaks into 3% and 8% live catalyst, and catalyst activity still encloses and reaches the activity level that can be used for former reaction process; And add-on is 25% and 40% o'clock, and catalyst activity can reach 92% and 95%, can be used for former reaction process.To activity is the regenerated catalyst of live catalyst 87%, sneaks into the live catalyst more than 3%, can be used for former reaction process.
Claims (10)
1, a kind of using method of regenerated catalyst, it is characterized in that comparing the live catalyst activity be to sneak into the similar live catalyst that accounts for catalyzer cumulative volume 1%～50% in the regenerated catalyst more than 75%, carry out activity rating then, when the performance of mixed catalyst reaches requiring of former reaction, be used for former reaction process, when the performance of mixed catalyst was lower than requiring of former reaction, degradation used this catalyzer.
2, according to the described method of claim 1, the activity that it is characterized in that described regenerated catalyst is that live catalyst is active more than 80%, and the live catalyst of sneaking into is 2%～30% of a catalyzer cumulative volume.
3, according to the described method of claim 1, it is characterized in that described catalyzer is a hydrocracking catalyst, when the activity of regeneration hydrocracking catalyst is the 85%-90% of live catalyst, after sneaking into the live catalyst that accounts for catalyzer cumulative volume 2%-15%, the activity of mixed catalyst reaches more than 90% of live catalyst, is used for former reaction process.
4, according to the described method of claim 3, the amount that it is characterized in that described live catalyst of sneaking into is 5%～10% of a catalyzer cumulative volume.
5, according to the described method of claim 1, it is characterized in that described catalyzer is a hydrocracking catalyst, when the activity of regeneration hydrocracking catalyst is the 80%-85% of live catalyst, after sneaking into the live catalyst that accounts for catalyzer cumulative volume 10%-50%, the activity of mixed catalyst reaches more than 90% of live catalyst, is used for former reaction process.
6,, it is characterized in that the described live catalyst mixed volume that is used for former reaction process is 20%～30% of a catalyzer cumulative volume according to the described method of claim 5.
7, according to the described method of claim 1, it is characterized in that described catalyzer is a Hydrobon catalyst, when the activity of regeneration Hydrobon catalyst is the active 90%-93% of live catalyst, sneak into the live catalyst that accounts for catalyzer cumulative volume 1%～10%, the activity of mixing rear catalyst is that live catalyst is active more than 93%, is used for former reaction process.
8,, it is characterized in that described live catalyst mixed volume is 3%～7% of a catalyzer cumulative volume according to the described method of claim 7.
9, according to the described method of claim 1, it is characterized in that described catalyzer is a Hydrobon catalyst, when the activity of regeneration Hydrobon catalyst is the 85%-90% of live catalyst, sneak into the live catalyst that accounts for catalyzer cumulative volume 15%～50%, mixed catalyst activity reaches more than 93% of live catalyst, is used for former reaction process; Or sneak into the live catalyst that accounts for catalyzer cumulative volume 5%-15%, and mixed catalyst activity is below 93% of live catalyst, degradation uses this mixed catalyst.
10, according to the described method of claim 9, it is characterized in that the described live catalyst mixed volume that is used for former reaction process is the 20%-30% of catalyzer cumulative volume, the live catalyst mixed volume that degradation uses is the 8%-12% of catalyzer cumulative volume.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02133143 CN1202211C (en) | 2002-10-10 | 2002-10-10 | Use method of reduced catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02133143 CN1202211C (en) | 2002-10-10 | 2002-10-10 | Use method of reduced catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1488714A CN1488714A (en) | 2004-04-14 |
| CN1202211C true CN1202211C (en) | 2005-05-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02133143 Expired - Lifetime CN1202211C (en) | 2002-10-10 | 2002-10-10 | Use method of reduced catalyst |
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| Country | Link |
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| CN (1) | CN1202211C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6420961B2 (en) * | 2014-03-27 | 2018-11-07 | 出光興産株式会社 | Recycling method of heavy oil desulfurization catalyst |
| CN106675645B (en) * | 2015-11-11 | 2018-03-16 | 中国石油化工股份有限公司 | A kind of catalytic diesel oil hydroconversion process grading method of catalyst |
| CN106675636B (en) * | 2015-11-11 | 2018-04-10 | 中国石油化工股份有限公司 | A kind of catalytic diesel oil hydroconversion process |
| CN107141220A (en) * | 2017-05-10 | 2017-09-08 | 河南神马尼龙化工有限责任公司 | A kind of method for persistently keeping hexamethylene diamine production catalyst performance |
| CN120037995A (en) * | 2023-11-24 | 2025-05-27 | 中国石油天然气股份有限公司 | A method for regenerating a deactivated hydrogenation catalyst |
-
2002
- 2002-10-10 CN CN 02133143 patent/CN1202211C/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| CN1488714A (en) | 2004-04-14 |
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Granted publication date: 20050518 |