CN100494322C - Method for starting operation of catalyst for hydrocracking in oxidation state - Google Patents
Method for starting operation of catalyst for hydrocracking in oxidation state Download PDFInfo
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- CN100494322C CN100494322C CNB2006101354329A CN200610135432A CN100494322C CN 100494322 C CN100494322 C CN 100494322C CN B2006101354329 A CNB2006101354329 A CN B2006101354329A CN 200610135432 A CN200610135432 A CN 200610135432A CN 100494322 C CN100494322 C CN 100494322C
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Abstract
This invention relates to a start-up method for oxidation-state hydrocracking catalyst used in oil refinery process. The method comprises: loading the oxidation-state hydrocracking catalyst into a reactor, introducing nitrogen to replace air in the reactor and pipelines, pressurizing to meet the pressure requirement of hydrocracking, switching to hydrogen after nitrogen flow is stable, raising the temperature of the catalyst bed to meet the temperature requirement of catalyst reduction after hydrogen flow is stable, keeping the temperature, adjusting the temperature of the catalyst bed to meet the temperature requirement of hydrocracking, adjusting hydrogen flux to meet the flux requirement of hydrocracking, and introducing hydrocarbon reactants. The method does not need pre-sulfurization of the catalyst with additional sulfurization agent, thus can avoid the problems caused by pre-sulfurization, and partially reduced catalyst has higher hydrocracking activity.
Description
Technical field
The present invention relates to a kind of catalyzer, especially relate to a kind of in oil refining process relevant oxidation state hydrocracking catalyst.
Background technology
In petroleum refining industry, hydrocracking is the important process process of being produced the high-quality light-weight oil product by mink cell focus, and its technological core is a catalyst system therefor.Hydrocracking catalyst is a kind of dual-function catalyst, has acid function and hydrogenating function concurrently.In present oil refining process, hydrocracking catalyst generally all carries out prevulcanized before use, promptly forces sulfuration, makes the activity of such catalysts component be in sulphided state, the catalyzer of this state can not poisoned by the sulphur in the reaction raw materials, and has the performance of certain cracking hydrogen molecule.In full scale plant and laboratory, hydrogenation catalyst sulfurized method mainly contains two kinds: a kind of is dry method, promptly injects vulcanizing agent in recycle hydrogen; A kind of is wet method, promptly under the condition that hydrogen exists, carries out catalyst vulcanization with the oil product that adds vulcanizing agent.In general the wet method prevulcanized is more common.Described a kind of typical method for pre-sulphuration among the patent CN1171430A, wherein vulcanizing agent is selected dithiocarbonic anhydride or dimethyl disulfide etc. for use, and the volume ratio of vulcanizing agent gas and catalyzer is generally 300～600; Sulfuration is carried out under normal pressure or high pressure, and general intensification and constant temperature program are to vulcanize 2～6h down at 200～240 ℃, vulcanize 8～12h down at 320～360 ℃ again.In addition, many catalyst presulfurizing methods have also been mentioned in the lot of documents at home and abroad.In recent years on the basis of successfully developing ebullated bed device outer regeneration technology, developed the outer pre-curing technology of ebullated bed device as TRICAT company again, this technology is to utilize hydrogen sulfide and hydrogen to carry out prevulcanized in ebullated bed reactor; Also have many catalyst Co. that vulcanizing agent is improved, " actiCAT " catalyzer is added in the hydrogenator, the vulcanization reaction process of carrying out in the presence of hydrogen is called " activation " process.
But pre-vulcanization process always exists a series of shortcoming: need special-purpose prevulcanized equipment and instrument 1.; 2. sulfidation is longer, extension fixture on-stream time; 3. vulcanizing agent and reaction product H2S thereof are hazardous and noxious substances.
Summary of the invention
Purpose of the present invention aims to provide a kind of the employing under the existing hydrocracking catalyst condition, need not to carry out the start-up method of oxidation state hydrocracking catalyst of the prevulcanized of catalyzer.
The step of start-up method of the present invention is as follows:
1) under the room temperature normal pressure, the oxidation state hydrocracking catalyst packed in the reactor;
2) feed in the nitrogen replacement reactor and the air in the pipeline before and after the reactor, reactive system progressively adherence pressure to the required pressure of hydrocracking reaction;
3) progressively switch hydrogen behind the steady air current, the temperature that promotes beds after hydrogen flowing quantity is stable more gradually is to required catalyst reduction temperature, constant temperature 1～5h is adjusted to the required temperature of hydrocracking reaction with bed temperature, and hydrogen flowing quantity is adjusted to the required flow of hydrocracking reaction;
4) progressively cut the reacted hydrocarbon raw material at last.
In reactor process that the oxidation state hydrocracking catalyst is packed into, notice that packing density should be even.
In step 2) in, its volume space velocity of described nitrogen is 1000～3000h
-1, the nitrogen replacement time is 4～10h.Reactive system reaction pressure 1.0～10.0MPa.
In step 3), particularly determine by sulphur content, purpose product requirement, catalyst performance and hydrocracking reaction condition by the hydrocarbon feed character of reacting for the reducing program of catalyzer, and controlled by modulation reduction temperature and recovery time, catalyst reduction pressure equals hydrocracking reaction pressure 1.0～10.0MPa, and the catalyst reduction temperature is 200～400 ℃.
Step 3) and 4) in, hydrocracking reaction pressure, temperature of reaction, hydrogen hydrocarbon volume ratio and hydrocarbon charging air speed are determined by hydrocarbon feed character, purpose product requirement and the catalyst performance of reaction.Be generally: reaction pressure 1.0～10.0MPa, 270～400 ℃ of temperature of reaction, hydrogen hydrocarbon volume ratio 600～1800, liquid hydrocarbon feed volume space velocity 1.0～4.0h
-1Described reacted hydrocarbon raw material can be the employed various raw materials of common hydrocracking, comprise carbon atom number in the molecule greater than straight-chain paraffin of 6 and composition thereof, and described straight-chain paraffin and the other types organism mixture of organosulfur compound and organic nitrogen compound particularly.
The sulphided state catalyzer has excellent sulfur poisoning-resistant ability, but its hydrogenation performance (being cracking hydrogen molecule and the ability that makes it to be in the medium tenacity adsorbed state) is lower; And reduction or the very high catalyzer of reducing degree have good hydrogenation performance but are easily poisoned by the sulphur in the reaction feed fully.Therefore, the intermediateness that between above-mentioned two kinds of extremities, has partial reduction.When hydrogenation catalyst is in this intermediateness, not only keep higher hydrogenation performance but also have stronger sulfur poisoning-resistant ability.The present invention utilizes this characteristic, in the process of going into operation, make catalyzer be in the intermediateness of partial reduction, need not to add again vulcanizing agent the catalyzer of oxidation state is carried out prevulcanized (forcing sulfuration), thereby avoided some problems of bringing by prevulcanized, and the catalyzer of partial reduction have higher hydrogenation cracking activity and middle runnings selectivity of product preferably in hydrocracking reaction.
Embodiment
The present invention is further illustrated below by embodiment.
Embodiment 1:
The hydrocracking catalyst that will contain heteropolyacid and with silicon-dioxide be carrier is packed in the reaction tubes, feeds nitrogen, and volume space velocity is 2000h
-1, continue 6h, reactive system progressively adherence pressure checks that to 2.0MPa air tight back introduces hydrogen, close the lasting 2h of nitrogen after, reactive system is warming up to 300 ℃, temperature rise rate is 2 ℃ of min
-1, keep 1h, at stable hydrogen volume air speed 2000h
-1Under cut n-decane, its volume space velocity is 2.5h
-1, begin collected specimens behind the reaction 4h, detect hydrogenation cracking activity and the selectivity of catalyzer under reaction conditions.Hydrogenation cracking activity is represented by the transformation efficiency of n-decane, and selectivity is designated as the C5+ selectivity by " the alkane mole number that contains 5 carbon atoms and 5 above carbon atoms in the product is divided by the product total mole number " expression.This be because, in hydrocracking process, wish that split product is many and the second pyrolysis product is few, when being the reacted hydrocarbon raw material with the n-decane, the alkane that contains 5 carbon atoms and 5 above carbon atoms in the product all is a split product, so the C5+ selectivity has characterized the relative quantity of a split product in the product.Hydrogenation cracking activity and the selectivity of catalyzer under reaction conditions sees Table 1.
Embodiment 2:
In embodiment 1, change the reacted hydrocarbon raw material into n-dodecane solution, i.e. the cost example.Hydrogenation cracking activity is represented by the transformation efficiency of n-dodecane, and selectivity is designated as the C6+ selectivity by " the alkane mole number that contains 6 carbon atoms and 6 above carbon atoms in the product is divided by the product total mole number " expression.This be because, in hydrocracking process, wish that split product is many and the second pyrolysis product is few, when being the reacted hydrocarbon raw material with the n-dodecane, the alkane that contains 6 carbon atoms and 6 above carbon atoms in the product all is a split product, so the C6+ selectivity has characterized the relative quantity of a split product in the product.Hydrogenation cracking activity and the selectivity of catalyzer under reaction conditions sees Table 1.
Embodiment 3:
In embodiment 1, change the reacted hydrocarbon raw material into the mixing solutions of n-dodecane and n-decane mass ratio 1:1, i.e. cost example.Hydrogenation cracking activity is represented by the transformation efficiency of mixed solution, and selectivity is designated as the C5+ selectivity by " the alkane mole number that contains 5 carbon atoms and 5 above carbon atoms in the product is divided by the product total mole number " expression.Hydrogenation cracking activity and the selectivity of catalyzer under reaction conditions sees Table 1.
Embodiment 4:
In embodiment 1, change the reacted hydrocarbon raw material into sulfur-bearing 300mgL
-1(providing) and nitrogenous 85mgL by thiophene
-1The n-decane solution of (providing), i.e. cost example by pyridine.Hydrogenation cracking activity and the selectivity of catalyzer under reaction conditions sees Table 1.
Embodiment 5:
In embodiment 1, hydrocracking catalyst is replaced by contains the commodity hydrocracking catalyst that molecular sieve is carrier with the aluminum oxide, i.e. cost example.Hydrogenation cracking activity and the selectivity of catalyzer under reaction conditions sees Table 1.
Embodiment 6:
In embodiment 1, hydrocracking catalyst is replaced by to contain heteropolyacid be the hydrocracking catalyst of carrier, i.e. cost example with the aluminum oxide.Hydrogenation cracking activity and the selectivity of catalyzer under reaction conditions sees Table 1.
Embodiment 7:
In embodiment 1, change hydrocracking reaction pressure into 5.0MPa, i.e. the cost example.Hydrogenation cracking activity and the selectivity of catalyzer under reaction conditions sees Table 1.
Comparative example 1-7:
In all embodiments, hydrocracking catalyst carries out prevulcanized according to the described typical method of patent CN1171430A to catalyzer, corresponding comparative example.Concrete operational condition is: sulfiding gas is that volume ratio is 5/95 CS2/H2, and its volume space velocity is 5000h
-1, vulcanize 3h down at 230 ℃, vulcanize 10h down at 340 ℃.Hydrogenation cracking activity and the selectivity of catalyzer under reaction conditions sees Table 1.
The reactive behavior and the selectivity of each routine catalyzer of table 1 gather
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | |
| Feed stock conversion % | 89 | 85 | 88 | 52 | 92 | 91 | 95 |
| Selectivity % | 70 | 71 | 72 | 68 | 69 | 72 | 69 |
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | |
| Feed stock conversion % | 52 | 49 | 50 | 31 | 33 | 54 | 60 |
| Selectivity % | 71 | 70 | 69 | 64 | 70 | 70 | 66 |
By table 1 as seen: adopt start-up method of the present invention under identical reacted hydrocarbon raw material, reaction conditions and same catalyzer situation, higher hydrogenation cracking activity to be arranged.
Claims (5)
1. the start-up method of an oxidation state hydrocracking catalyst is characterized in that its step is as follows:
1) under the room temperature normal pressure, the oxidation state hydrocracking catalyst packed in the reactor;
2) feed the air that reaches in the nitrogen replacement reactor in the pipeline of reactor front and back, the reactive system adherence pressure is to the required pressure of hydrocracking reaction;
3) switch hydrogen behind the steady air current, temperature to the required catalyst reduction temperature that promotes beds after hydrogen flowing quantity is stable again is 200～400 ℃, constant temperature 1～5h, bed temperature is adjusted to the required temperature of hydrocracking reaction, and hydrogen flowing quantity is adjusted to the required flow of hydrocracking reaction;
4) cut the reacted hydrocarbon raw material at last.
2. the start-up method of a kind of oxidation state hydrocracking catalyst as claimed in claim 1 is characterized in that step 2) in, the nitrogen volume space velocity is 1000～3000h
-1, the nitrogen replacement time is 4～10h, reactive system reaction pressure 1.0～10.0MPa.
3. the start-up method of a kind of oxidation state hydrocracking catalyst as claimed in claim 1 is characterized in that in the step 3), catalyst reduction pressure 1.0～10.0MPa.
4. the start-up method of a kind of oxidation state hydrocracking catalyst as claimed in claim 1, it is characterized in that step 3) and 4) in, hydrocracking reaction pressure 1.0～10.0MPa, 270～400 ℃ of temperature of reaction, hydrogen hydrocarbon volume ratio 600～1800, liquid hydrocarbon feed volume space velocity 1.0～4.0h
-1
5. the start-up method of a kind of oxidation state hydrocracking catalyst as claimed in claim 1, it is characterized in that in step 4), described reacted hydrocarbon raw material is the employed various raw materials of hydrocracking, comprise carbon atom number in the molecule greater than straight-chain paraffin of 6 and composition thereof, and the mixture of described straight-chain paraffin and organosulfur compound and organic nitrogen compound.
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| CNB2006101354329A CN100494322C (en) | 2006-12-31 | 2006-12-31 | Method for starting operation of catalyst for hydrocracking in oxidation state |
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| CNB2006101354329A CN100494322C (en) | 2006-12-31 | 2006-12-31 | Method for starting operation of catalyst for hydrocracking in oxidation state |
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| CN100494322C true CN100494322C (en) | 2009-06-03 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101492613B (en) * | 2008-01-23 | 2012-11-21 | 中国石油化工股份有限公司 | Start working method for hydrocracking process |
| CN102051203B (en) * | 2009-10-27 | 2012-09-12 | 中国石油化工股份有限公司 | Start-up method for external presulfurizing catalyst |
| CN102311762B (en) * | 2010-07-07 | 2014-01-22 | 中国石油化工股份有限公司 | Suspension bed heavy oil hydrogenation process start-up method |
| CN102465005A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Application method of second-kind active site hydrogenation catalyst |
| CN103059969B (en) * | 2011-10-21 | 2014-12-31 | 中国石油化工股份有限公司 | Startup passivation method of hydrocracking catalyst |
| CN109988626B (en) * | 2017-12-29 | 2021-07-09 | 中国石油化工股份有限公司 | Flexible two-stage hydrocracking process |
| CN112574775B (en) * | 2019-09-30 | 2022-07-12 | 中国石油化工股份有限公司 | Start-up method and application of hydrocracking catalyst |
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|---|---|---|---|---|
| US5888377A (en) * | 1997-12-19 | 1999-03-30 | Uop Llc | Hydrocracking process startup method |
| CN1297020A (en) * | 1999-11-17 | 2001-05-30 | 中国石油化工集团公司 | Process for restarting reforming equipment filled with bimetal/multi-metal catalyst |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5888377A (en) * | 1997-12-19 | 1999-03-30 | Uop Llc | Hydrocracking process startup method |
| CN1297020A (en) * | 1999-11-17 | 2001-05-30 | 中国石油化工集团公司 | Process for restarting reforming equipment filled with bimetal/multi-metal catalyst |
Non-Patent Citations (2)
| Title |
|---|
| 齐鲁石化公司1.4Mt/a加氢裂化装置的开工及运行. 孙振光，王智.石油炼制与化工，第VOL.34卷第NO.11期. 2003 |
| 齐鲁石化公司1.4Mt/a加氢裂化装置的开工及运行. 孙振光，王智.石油炼制与化工，第VOL.34卷第NO.11期. 2003 * |
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Assignee: Cangzhou Huahai Refining Chemical Co.,Ltd. Assignor: Xiamen University Contract record no.: 2011130000150 Denomination of invention: Method for starting operation of catalyst for hydrocracking in oxidation state Granted publication date: 20090603 License type: Exclusive License Open date: 20070725 Record date: 20111008 |
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