CN103102929B - Wet startup sulfuration method of hydrocracking unit - Google Patents
Wet startup sulfuration method of hydrocracking unit Download PDFInfo
- Publication number
- CN103102929B CN103102929B CN201110353213.9A CN201110353213A CN103102929B CN 103102929 B CN103102929 B CN 103102929B CN 201110353213 A CN201110353213 A CN 201110353213A CN 103102929 B CN103102929 B CN 103102929B
- Authority
- CN
- China
- Prior art keywords
- oil
- temperature
- sulfuration
- hydrogen sulfide
- vulcanizing agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a wet startup sulfuration method of a hydrocracking unit. The method comprises the following steps that: (a) light fraction startup oil is introduced at a low temperature; (b) a vulcanizing agent is introduced when a temperature at an inlet of a reactor reaches a decomposition temperature of the vulcanizing agent; (c) after hydrogen sulfide penetrates a catalyst bed in the reactor, heating is carried out according to a conventional hydrogenation catalyst sulfuration process, then heavy fraction sulfur-containing startup oil is introduced instead when the catalyst bed reaches a temperature of 235 to 300 DEG C, liquefied ammonia is introduced at the same time, and introduction of the vulcanizing agent is stopped; (d) after introduction of the heavy fraction sulfur-containing startup oil, final sulfuration of a catalyst is completed by using hydrogen sulfide obtained in a hydrogenolysis reaction of a sulfide in the startup oil; and (e) raw oil is directly introduced instead step by step after sulfuration is finished, and when 60 to 85% of raw oil is introduced, introduction of liquefied ammonia is stopped and normal production is started. Compared with the prior art, the method provided by the invention enables startup time to be shortened while guaranteeing performance of the catalyst and realizes safe and smooth startup.
Description
Technical field
The invention belongs to the working method of oil Refining Technologies, particularly relate to a kind of wet method sulfuration start-up method of hydrogenation unit.
Background technology
Along with environmental regulation increasingly stringent in global range, the demand of clean light clean fuel is got more and more, hydrogen addition technology is the effective means of cleaning product, and therefore hydrogenation unit has become the standard configuration of refinery, and the hydrogenation unit in oil refining enterprise is on the increase.
In hydrogen addition technology use catalyzer for dual-function catalyst, its Hydrogenation comes from active metal, active metal is divided into precious metal and base metal two kinds usually, and base metal mainly comprises VI B and VIII race's metal (as Mo, W, Ni and Co etc.) element, in commodity hydrogenation catalyst, these metals normally exist with the form of oxidation state.Because the Hydrogenation of oxidation state metal and atoms metal is lower, only be translated into sulphided state and just there is higher Hydrogenation, therefore in order to make the performance of hydrogenation catalyst reach best, need to carry out sulfuration (sometimes also claiming prevulcanized) to catalyzer before use.
US4177136 discloses the hydroprocessing processes with elementary sulfur, hydrogenation catalyst being carried out to sulfuration, carries out sulfuration with elementary sulfur to catalyzer.The method shortcoming is that solid element sulphur is all converted into hydrogen sulfide at a lower temperature, but catalyzer at low temperatures can not sulfuration complete, can not supply catalyzer enough sulphur during high temperature, namely the feed speed of hydrogen sulfide can not control accurately, makes the cure efficiency of catalyzer poor.
CN1082591A discloses a kind of processing hydrocarbons catalyst vulcanization method, and the method adds vulcanizing agent by solvent, and all or part of a kind of component or the similar components containing alkene and alkene cut (such as plant oil) of this solvent.Its shortcoming is that the chain olefinic constituent separately added in solvent is difficult to obtain in refinery, and easy polymerization coking on hydroprocessing catalysts during comparatively high temps sulfuration, affects the activity of catalyzer.
CN1362289A discloses a kind of vulcanization process of hydrogenation catalyst, and the method by arranging the one or more sulfuration of hydrogen sulfide generator for catalyzer of having loaded the S-contained substance such as sulfurous iron ore or elemental sulfur before hydrogenator.Its shortcoming needs to build a reactor separately, and need to purify hydrogen sulfide, need the make-up hydrogen compressor of hydrogen sulfide corrosion resistant, sulphur iron ore also needs subsequent disposal simultaneously.
Usually gas-phase presulfiding method is used during the catalyst vulcanization that hydroeracking unit uses.Gas-phase presulfiding also claims dry pre-sulfiding, sulfidation only uses vulcanizing agent, need to introduce when reaction bed temperature being reduced to safety temperature the low nitrogen oil that goes into operation after sulfuration terminates and carry out catalyst irrigation, then heat up and progressively switch stock oil, on-stream time is longer, under prerequisite completely smoothly, usually from sulfuration at least need more than 6 days to complete swap-in stock oil, and exist and be easy to that larger temperature fluctuation etc. occurs and be unfavorable for quiet run factor.
Prior art hydroeracking unit go into operation in sulfidation, usually use dry pre-sulfiding (conventional wet method sulfuration is unwell to hydroeracking unit and goes into operation sulfuration, and the final curing temperature that can reach is low, and there is the potential safety hazards such as temperature runaway).Time dry pre-sulfiding, vulcanizing agent is injected during temperature height, hydrogen sulfide cannot be produced at a lower temperature, there is not the sulfidation under low temperature in catalyzer, for hydrogenation catalyst, the performance of catalyst performance can be affected, the catalyzer particularly containing easy decomposition components, larger to the activity influence of catalyzer.In addition, in order to realize steady swap-in stock oil after dry pre-sulfiding end, need reaction bed temperature to be reduced to less than 200 DEG C, even reach less than 150 DEG C, then introduce low nitrogen in turn to go into operation oil and note ammonia passivation, then heat up and substep swap-in stock oil, whole sulfuration is longer for on-stream time.The present invention carries out wet method sulfuration by using go into operation oil and vulcanizing agent of lighting end when low temperature, go into operation oily in the sulfurating stage swap-in last running that temperature is higher and stop using vulcanizing agent, the hydrogen sulfide relying on sulfide hydrogenolysis to obtain has continued sulfidation, inject liquefied ammonia simultaneously and carry out catalyst deactivation, sulfuration terminates rear direct substep swap-in stock oil, curtailment of operation under the prerequisite ensureing catalyst vulcanization effect, realize the operation that steadily goes into operation simultaneously.
Summary of the invention
For the deficiencies in the prior art, in order to the quiet run of curtailment of operation and sulfidation, the invention provides a kind of hydroeracking unit wet method vulcanization process, the curtailment of operation under the prerequisite ensureing catalyst vulcanization effect, realize the operation that steadily goes into operation simultaneously.
The wet method sulfuration start-up method of hydroeracking unit of the present invention comprises the steps:
A () is introduced lighting end and to be gone into operation oil when low temperature;
B () introduces vulcanizing agent when reactor inlet temperature reaches the temperature of vulcanizing agent decomposition;
C () hydrogen sulfide penetrates reactor catalyst bed after, hydrogenation catalyst sulfidation heats up routinely, and after beds reaches 235 ~ 300 DEG C, swap-in last running sulfur-bearing goes into operation oil, introduces liquefied ammonia simultaneously, and stops introducing vulcanizing agent;
D () introducing last running sulfur-bearing goes into operation after oil, the hydrogen sulfide obtained by the sulfide hydrogenolysis gone into operation in oil completes the final sulfidation of catalyzer;
E () sulfuration terminates rear direct substep swap-in stock oil, stop introducing liquefied ammonia, proceed to normal production when swap-in 60% ~ 85% stock oil (stock oil account for stock oil and last running sulfur-bearing go into operation the mass ratio of oil) time.
In the inventive method step (a), the lighting end oil that goes into operation used when hydroeracking unit goes into operation is the petroleum fractions being rich in stable hydrocarbon, as straight run boat coal, straight-run diesel oil etc., also can for the boat coal obtained through deep hydrofinishing, or the boat coal etc. that hydrocracking obtains, the μ g/g(≯ expression in nitrogen content ≯ 200 in oil that requires to go into operation is not more than, and is namely less than or equal to, lower same), preferably ≯ 100 μ g/g.Introduce lighting end go into operation oil time reactor inlet temperature be 50 ~ 150 DEG C.Sulfuration start-up process carries out in presence of hydrogen.In sulfidation, hydrogen to oil volume ratio is generally 100:1 ~ 2000:1.In sulfuration start-up process, during liquid, body air speed is generally 0.1 ~ 10h
-1.
In the inventive method step (b), vulcanizing agent is the vulcanizing agent that hydrogenation process routine uses, and is generally liquid sulfocompound, requires that hydrogenolysis temperature is higher than 140 DEG C, be generally 150 DEG C ~ 400 DEG C, concrete as CS
2, DMDS(dimethyl disulfide), SulfrZol
?54(commercial goods vulcanizing agent, effective constituent is C
8h
18s
4), diethyl disulphide, dipropyl disulfide etc. also can be transports and store safer other polysulfide etc.The sulfuration dosage introduced in step (b) is that 500 ~ 6000 μ L/L determine by beds entrance hydrogen sulfide in gas phase content.
In the inventive method step (c), hydrogen sulfide penetrates beds, refers to that the concentration of hydrogen sulfide in reactor outlet gas phase reaches 1000 more than μ L/L.
In the inventive method step (c), after hydrogen sulfide penetrates beds, conventional hydrogenation catalyst sulfidation heat-up rate is generally ≯ 10 DEG C/h, when the temperature of beds is increased to 230 ± 5 DEG C, constant temperature sulfuration more than 8 hours, controls reactor outlet hydrogen sulfide in gas phase concentration 1000 ~ 7000 μ L/L around here, the temperature of beds is increased to certain temperature by then ≯ 8 DEG C/h speed, i.e. target temperature, is generally 235 ~ 300 DEG C, preferably 240 ~ 280 DEG C.
In the inventive method step (c), the last running sulfur-bearing used when hydrogenation unit the goes into operation oil that goes into operation is the petroleum fractions of sulfur-bearing, as a kind of or mixed several mixture in straight-run diesel oil, coker gas oil, catalytic cracking diesel oil etc., in general last running sulfur-bearing goes into operation oily sulphur content higher than 0.3%(quality), preferably higher than 0.6%.
In the inventive method step (c), swap-in last running sulfur-bearing goes into operation after oil, injects liquefied ammonia, and liquefied ammonia injection rate is 0.3% ~ 2.0% to determine by ammonia mass concentration in the isolated aqueous phase of high-pressure separator, is preferably 0.4% ~ 1.8%.In described high-pressure separator in hydroeracking unit, the material after reactor through cooling, water filling, after air cooler, the gas-liquid separator entered, is separated into gas phase, aqueous phase and oil phase, is content well known to those skilled in the art.
In the inventive method step (d), introducing last running sulfur-bearing goes into operation after oil, with the heat-up rate of 1 ~ 10 DEG C/h, the temperature of beds is increased to 290 ± 5 DEG C, control reactor outlet hydrogen sulfide in gas phase concentration 5000 ~ 12000 μ L/L around here, reach steady to make reaction bed temperature and for reaching in next stage circulation gas the requirement controlling concentration of hydrogen sulfide, preferably constant temperature 0.1 ~ 4 hour at this temperature.And then with the heat-up rate of 3 ~ 18 DEG C/h, the temperature of beds is increased to 320 ~ 360 DEG C, and at the temperature be finally raised to constant temperature at least 8 hours, control concentration 10000 ~ 30000 μ L/L of reactor outlet hydrogen sulfide in gas phase during this period, complete above-mentioned steps, namely complete the pre-vulcanization process of catalyzer.
In the inventive method step (e), after sulfidation terminates, divide and progressively increase reactor feed Raw oil ratio example swap-in stock oil for 2 ~ 6 times, this process is well known to those skilled in the art.As can be (be 25 quality % in charging be specifically stock oil according to 25% stock oil respectively, 75 quality % are that last running sulfur-bearing goes into operation oil, lower with), 50% stock oil, 75% stock oil and 100% stock oil substep swap-in stock oil, more than 2 hours, general interval during each stock oil of swap-in.Stop after swap-in 75% stock oil injecting liquefied ammonia.Then the requirement that temperature of reaction reaches cracking conversion rate is adjusted, last swap-in 100% stock oil.
In the inventive method, circulation gas is the high pressure gas being rich in hydrogen in start-up process, and hydrogen purity (volume) is not less than 50%, is preferably not less than 60%, is preferably not less than 70%.
In the inventive method, the pressure of sulfidation can be working pressure, also can comparatively working pressure is low, is preferably 50% ~ 100% of design operation pressure, is preferably 75% ~ 100% of design pressure.
In the inventive method, hydroeracking unit generally comprises hydrofining section and hydrocracking section (serial hydrocracking technique), and sometimes also have a hydrocracking section (single-stage hydrocracking technique), stock oil is generally vacuum distillate.
Embodiment
Method of the present invention is specific as follows: first introduce lighting end when low temperature and to go into operation oil, then heat up, vulcanizing agent is introduced when temperature reaches vulcanizing agent decomposition temperature, vulcanizing agent hydrogenolysis obtains hydrogen sulfide, continue to heat up and wait for that hydrogen sulfide penetrates beds, according to the injection rate of the requirement adjustment vulcanizing agent of hydrogen sulfide content after hydrogen sulfide penetrates in a large number, be warming up to 230 DEG C with ≯ 5 DEG C/h speed simultaneously, constant temperature sulfuration 8 hours, then 3 ~ 6 DEG C/h speed is warming up to 235 ~ 300 DEG C, swap-in heavy sulfur-bearing goes into operation oil, 330 ~ 370 DEG C are warming up to again with 4 ~ 8 DEG C/h speed, and constant temperature 8 hours at this temperature, complete the pre-vulcanization process of catalyzer.Then direct substep swap-in and stopping liquefied ammonia, proceed to normal production.In Hydrocracking Units start-up process of the present invention, other content is well known to those skilled in the art.
Particular case of the present invention is further illustrated below by embodiment.Catalyzer FF-46 is the wax oil cut fraction hydrogenation process catalyzer of China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute's development and production, and catalyzer FC-50 is the wax oil cut fraction hydrogenation cracking catalyst of China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute's development and production.
Table 1 stock oil main character.
| Stock oil | Iran VGO |
| Density (20 DEG C)/gcm -3 | 0.9135 |
| Boiling range/DEG C | 350~545 |
| Sulphur content, wt% | 1.74 |
| Nitrogen content, μ gg -1 | 1535 |
| Aromatic hydrocarbons, wt% | 43.8 |
Table 2 embodiment processing condition and test-results.
| Processing condition | Embodiment 1 | Reference example 1 | Embodiment 2 | Embodiment 3 |
| Catalyzer | FF-46/FC-50 | FF-46/FC-50 | FF-46/FC-50 | FF-46/FC-50 |
| Vulcanization process | Present method | Dry pre-sulfiding | Present method | Present method |
| Vulcanizing agent | ?DMDS | ?DMDS | CS 2 | CS 2 |
| Pressure/MPa | 15.0 | 15.0 | 13.0 | 10.0 |
| Introduce lighting end go into operation oil temperature/DEG C | 80 | — | 120 | 50 |
| Change to last running sulfur-bearing go into operation oil temperature/DEG C | 270 | — | 240 | 260 |
| Final curing temperature/DEG C | 370 | 370 | 360 | 350 |
| Go into operation total time/h | 66 | 144 | 58 | 62 |
| Sulfuration rear catalyst activity rating condition and result | ? | ? | ? | ? |
| Stock oil | Iran VGO | Iran VGO | Iran VGO | Iran VGO |
| Reaction pressure/MPa | 15.7 | 15.7 | 15.7 | 15.7 |
| Pretreatment section operational condition | ? | ? | ? | ? |
| Catalyzer | FF-46 | FF-46 | FF-46 | FF-46 |
| Volume space velocity/h -1 | 1.0 | 1.0 | 1.0 | 1.0 |
| Hydrogen to oil volume ratio | 1000 | 1000 | 1000 | 1000 |
| Average reaction temperature/DEG C | 386 | 386 | 386 | 386 |
| Generate oily nitrogen content/μ gg -1 | 4.5 | 5.0 | 6.2 | 7.3 |
| Cracking zone operational condition | ? | ? | ? | ? |
| Catalyzer | FC-50 | FC-50 | FC-50 | FC-50 |
| Volume space velocity/h -1 | 1.5 | 1.5 | 1.2 | 1.8 |
| Hydrogen to oil volume ratio | 1500 | 1500 | 1200 | 1800 |
| Average reaction temperature/DEG C | 385 | 385 | 380 | 385 |
| Per pass conversion, % | 66 | 66 | 70 | 60 |
As can be seen from embodiment, adopt the catalyst vulcanization method of the inventive method, not only effectively can play the activity of catalyzer, and can significantly curtailment of operation, improve the stability of start-up process.
Claims (10)
1. a wet method sulfuration start-up method for hydroeracking unit, is characterized in that comprising the steps:
A () is introduced lighting end and to be gone into operation oil when low temperature;
B () introduces vulcanizing agent when reactor inlet temperature reaches the temperature of vulcanizing agent decomposition;
C () hydrogen sulfide penetrates reactor catalyst bed after, hydrogenation catalyst sulfidation heats up routinely, after beds reaches 235 ~ 300 DEG C, swap-in last running sulfur-bearing goes into operation oil, last running sulfur-bearing goes into operation oily sulphur content higher than 0.3 quality %, introduce liquefied ammonia simultaneously, and stop introducing vulcanizing agent;
D () introducing last running sulfur-bearing goes into operation after oil, the hydrogen sulfide obtained by the sulfide hydrogenolysis gone into operation in oil completes the final sulfidation of catalyzer;
E () sulfuration terminates rear direct substep swap-in stock oil, stop introducing liquefied ammonia, proceed to normal production when swap-in 60% ~ 85% stock oil.
2. in accordance with the method for claim 1, it is characterized in that: in step (a), lighting end goes into operation oil is straight run boat coal, straight-run diesel oil, deep hydrofinishing obtain boat coal or the boat coal that hydrocracking obtains, requirement goes into operation nitrogen content ≯ 200 μ g/g in oil, introduce lighting end go into operation oil time reactor inlet temperature be 50 ~ 150 DEG C.
3. in accordance with the method for claim 1, it is characterized in that: in step (b), vulcanizing agent is the vulcanizing agent that hydrogenation process routine uses, and vulcanizing agent is selected from CS
2, DMDS, C
8h
18s
4, diethyl disulphide, dipropyl disulfide.
4. according to the method described in claim 1 or 3, it is characterized in that: the sulfuration dosage introduced in step (b) is that 500 ~ 6000 μ L/L determine by beds entrance hydrogen sulfide in gas phase content.
5. in accordance with the method for claim 1, it is characterized in that: in step (c), after hydrogen sulfide penetrates beds, conventional hydrogenation catalyst sulfidation heat-up rate is ≯ 10 DEG C/h, when the temperature of beds is increased to 230 ± 5 DEG C, constant temperature sulfuration more than 8 hours, control reactor outlet hydrogen sulfide in gas phase concentration 1000 ~ 7000 μ L/L around here, the temperature of beds is increased to 235 ~ 300 DEG C by then ≯ 8 DEG C/h speed.
6. in accordance with the method for claim 1, it is characterized in that: in step (c), the last running sulfur-bearing used when hydrogenation unit the goes into operation oil that goes into operation is the petroleum fractions of sulfur-bearing, is selected from a kind of or mixed several mixture in straight-run diesel oil, coker gas oil, catalytic cracking diesel oil.
7. according to the method described in claim 1 or 6, it is characterized in that: in step (c), swap-in last running sulfur-bearing goes into operation after oil, injects liquefied ammonia, and liquefied ammonia injection rate is 0.3% ~ 2.0% to determine by ammonia mass concentration in the isolated aqueous phase of high-pressure separator.
8. in accordance with the method for claim 1, it is characterized in that: in step (d), introducing last running sulfur-bearing goes into operation after oil, with the heat-up rate of 1 ~ 10 DEG C/h, the temperature of beds is increased to 290 ± 5 DEG C, control reactor outlet hydrogen sulfide in gas phase concentration 5000 ~ 12000 μ L/L around here, constant temperature 0.1 ~ 4 hour at this temperature; And then with the heat-up rate of 3 ~ 18 DEG C/h, the temperature of beds is increased to 320 ~ 360 DEG C, and at the temperature be finally raised to constant temperature at least 8 hours, control concentration 10000 ~ 30000 μ L/L of reactor outlet hydrogen sulfide in gas phase during this period, complete above-mentioned steps, namely complete the pre-vulcanization process of catalyzer.
9. in accordance with the method for claim 1, it is characterized in that: in step (e), after sulfidation terminates, divide and progressively increase reactor feed Raw oil ratio example swap-in stock oil for 2 ~ 6 times.
10. in accordance with the method for claim 1, it is characterized in that: hydroeracking unit comprises hydrofining section and hydrocracking section, or only have a hydrocracking section, stock oil is vacuum distillate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110353213.9A CN103102929B (en) | 2011-11-10 | 2011-11-10 | Wet startup sulfuration method of hydrocracking unit |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110353213.9A CN103102929B (en) | 2011-11-10 | 2011-11-10 | Wet startup sulfuration method of hydrocracking unit |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103102929A CN103102929A (en) | 2013-05-15 |
| CN103102929B true CN103102929B (en) | 2014-12-31 |
Family
ID=48311135
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110353213.9A Active CN103102929B (en) | 2011-11-10 | 2011-11-10 | Wet startup sulfuration method of hydrocracking unit |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103102929B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116059925A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Hydrogenation reaction rectification process starting method and hydrogenation reaction rectification device applying same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1335362A (en) * | 2000-07-24 | 2002-02-13 | 中国石油化工股份有限公司 | Sulfurizing method of hydrogenation catalyst |
| CN101492613A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Start working method for hydrocracking process |
-
2011
- 2011-11-10 CN CN201110353213.9A patent/CN103102929B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1335362A (en) * | 2000-07-24 | 2002-02-13 | 中国石油化工股份有限公司 | Sulfurizing method of hydrogenation catalyst |
| CN101492613A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Start working method for hydrocracking process |
Non-Patent Citations (1)
| Title |
|---|
| 韩崇仁.第十三章 工业装置操作技术.《加氢裂化工艺与工程》.中国石化出版社,2001,第827-833页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103102929A (en) | 2013-05-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103789007B (en) | Wet starting method of hydrocracking unit | |
| CN103059968B (en) | Vulcanization startup method of hydrocracking device | |
| CN105754637B (en) | A kind of start-up vulcanization method of hydrogenation catalyst | |
| CN102051205A (en) | In-situ presulfurization method of hydrogenation catalyst | |
| TW201247861A (en) | Hydroprocessing process using uneven catalyst volume distribution among catalyst beds in liquid-full reactors | |
| CN102311766A (en) | Class II active center hydrogenation catalyst start-up vulcanization method | |
| CN103789008B (en) | Starting method of hydrocracking unit | |
| CN102051204B (en) | Work starting method for hydrogenation process | |
| CN103100446B (en) | Startup sulfuration method of hydrogenation unit | |
| CN110653007B (en) | Hydrogenation catalyst start-up vulcanization method | |
| CN102641749B (en) | Prevulcanization method of hydrotreatment catalyst | |
| CN102041045B (en) | On-stream method of residual oil hydrogenation process | |
| CN103102929B (en) | Wet startup sulfuration method of hydrocracking unit | |
| CN103102931B (en) | Wet startup sulfuration method of hydrocracking unit | |
| CN102051203B (en) | Start-up method for external presulfurizing catalyst | |
| CN102311765B (en) | Startup sulfurization method for trickle bed class-II active center hydrogenation catalyst | |
| CN103100449B (en) | Startup sulfuration method of liquid phase circulation hydrogenation unit | |
| CN103100448B (en) | In-situ sulfuration method for hydrogenation catalyst | |
| CN103100447B (en) | Startup sulfuration method of hydrogenation unit | |
| CN103357449B (en) | A kind of catalyst vulcanization method of diesel oil hydrogenation handling process | |
| CN102443427A (en) | Start-up vulcanizing method of hydrocracking process | |
| CN102872922B (en) | Hydrofining catalyst vulcanization method | |
| CN103789009B (en) | Wet starting method of hydrocracking unit | |
| CN104650963B (en) | A kind of start-up method of FCC gasoline hydrogenation catalyst | |
| CN103789023B (en) | Hydroeracking unit start-up method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |