CN103789007B - Wet starting method of hydrocracking unit - Google Patents
Wet starting method of hydrocracking unit Download PDFInfo
- Publication number
- CN103789007B CN103789007B CN201210432669.9A CN201210432669A CN103789007B CN 103789007 B CN103789007 B CN 103789007B CN 201210432669 A CN201210432669 A CN 201210432669A CN 103789007 B CN103789007 B CN 103789007B
- Authority
- CN
- China
- Prior art keywords
- temperature
- oil
- methods according
- nitrogenous
- goes
- 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 starting method of a hydrocracking unit. A reaction zone of the hydrocracking unit is filled with a sulfurization type hydrogenation catalyst. The starting method comprises steps of heating starting oil through heat exchange to a certain temperature, passing the starting oil through a catalyst bed layer to raise the temperature of the catalyst bed layer to be 180+/-15 DEG C or higher by utilization of the heat of reactions during heat exchange and activation, blending a part of gas with a high olefin content into circulating gas, raising the temperature continuously to 230+/-15 DEG C by utilization of the heat of olefin hydrogenation reactions and activating at the constant temperature, introducing nitrogen-containing light distillate oil when the temperature is 245+/-15 DEG C, introducing nitrogen-containing heavy distillate oil instead when the temperature is 290+/-15 DEG C or higher, introducing raw oil instead step by step when the temperature is 320+/-15 DEG C, raising the temperature continuously by utilization of the heat of hydrogenation reactions of the raw oil, and finally adjusting the reaction temperature by the hydrogen cooling amount and a heat exchanger and shifting to normal production. Compared with the prior art, the starting method omits a heating furnace in the starting process of the hydrocracking unit and the starting process is smooth and steady.
Description
Technical field
The invention belongs to the working method of oil Refining Technologies, particularly relate to hydroeracking unit wet method start-up method.
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 producing 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.
Hydrocracking technology is the one in hydrogen addition technology, by one of heavy distillate important means being processed as cleaning product, hydrocracking technology generally with vacuum distillate or close distillate for raw material, produce high-quality petroleum naphtha, boat coal and diesel oil, hydrocracking tail oil is also steam cracking ethylene raw and the isomerization dewaxing Lube basic oil material feedstocks of high-quality simultaneously.The catalyzer that hydrocracking technology uses is dual-function catalyst, comprise cracking function and hydrogenating function, cracking function is provided by molecular sieve usually, and using at present is Y zeolite, Beta type molecular sieve, ZSM Series Molecules sieve, MCM Series Molecules sieve comparatively widely, and composite molecular screen etc.Its Hydrogenation comes from active metal, active metal is divided into precious metal and base metal two kinds usually, most importantly base metal, mainly comprise 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, just be only translated into sulphided state there is higher Hydrogenation, therefore in order to make the performance of hydrogenation catalyst reach best, need to carry out sulfuration to catalyzer before use.The prevulcanized of hydrogenation catalyst is divided into in-situ presulfurization and ex situ presulfiding two kinds usually: in-situ presulfurization is being first loaded in hydrogenator by hydrogenation catalyst, then adopt wet method or dry pre-sulfidingly carry out sulfuration, ex situ presulfiding refers to that catalyzer just carries out prevulcanized before being loaded into reactor, has sulfide type and sulphided state two kinds.No matter use in-situ presulfurization and ex situ presulfiding hydrogenation catalyst, hydrogenation unit can use liquid phase sulfuration (activation) start-up method.
Hydroeracking unit generally needs operation at relatively high temperatures, in hydrogenation unit start-up process, need device to be raised at normal temperatures comparatively high temps (being generally more than 320 DEG C), usual hydrogenation unit arranges process furnace, goes into operation and provide heat in production process for device.Hydrogenation reaction is generally strong exothermal reaction, in hydrogenation unit normal productive process, namely reactor outlet temperature, far above temperature in, now can realize the heating to reaction raw materials by heat exchange mode, if interchanger effect is enough, process furnace can not used when normal production completely.But in start-up process, owing to not entering normal hydogenation reaction, device heats up does not have origin of heat, and adopt miscellaneous equipment generally cannot reach required temperature, therefore start-up process needs to arrange process furnace.Process furnace is the high-temperature high-pressure apparatus in hydrogenation unit, and facility investment is very large, and process furnace only uses in start-up process, and utilization ratio of device is low, and furnace tubing is one of important sources increasing high-pressure system Pressure Drop.
CN200910188142.4 discloses the vulcanizing agent supply method of catalyst wet sulfidation, and the method is mainly for liquid phase circulation hydrogenation unit start-up process, and start-up process must have process furnace.CN200510047487.X discloses a kind of start-up method of FCC gasoline hydrogenating desulfurization Olefin decrease technology, the main selectoforming of the method generates oil as vulcanized oil, avoid the temperature rise that sulfidation produces, and be only applicable to the gasoline hydrogenation device containing molecular sieve catalyst.
US 5688736 discloses a kind of catalyst vulcanization method, forbids to use the oil that goes into operation containing alkene in start-up process.CN200910188114.2, CN200910204266.7, CN200810010242.3, CN200810010245.7, CN200910204248.9, CN200910204249.3 disclose the start-up method using sulfide type catalyst hydrogenation unit, these methods all require to use the few activation oil of olefin(e) centent to go into operation in start-up process, and the heat in catalyst activation process required for reactive system intensification is all by using process furnace to provide.The start-up method of CN 200910204283.0 Residue Hydrotreating Technology; the method discloses a kind of hydrogenation unit start-up method containing the agent of partial vulcanization type hydrogenation protecting; start-up process needs additional vulcanizing agent catalyst oxidation type hydrogenation catalyst to carry out prevulcanized, and needs process furnace to provide heat.
Go into operation for using the hydroeracking unit of presulfurization catalyst, topmost method introduces the activation oil that goes into operation, by heating and heating up according to certain heat-up rate, until substep swap-in stock oil during the initial reaction temperature of temperature close to stock oil, all need to use process furnace to provide the heat of reactive system temperature-rise period in start-up process, start-up process energy consumption is larger, start-up process cannot be realized for there is no the device of process furnace, and use process furnace can increase considerably the Pressure Drop of system and energization consumption, anhydrous liquid ammonia to be introduced in addition when temperature reaches certain temperature and carry out passivation, avoid hydrocracking catalyst initial activity too high and the raw hydrocracking reaction of fry dried food ingredients that causes going into operation, and realize steadily switching raw material wet goods start-up process.
The wet method of prior art hydrogenation unit goes into operation in sulfidation, needs to use process furnace to the heat providing reaction bed temperature to improve, and also needs to use anhydrous liquid ammonia to carry out catalyst deactivation.The heat that the present invention is produced by use low-temperature heat source, sulfide type catalyst reactivation process, introducing are rich in the reaction heat that alkene benzoline is obtained by reacting at a lower temperature, the next common finishing device start-up process of reaction heat utilizing stock oil hydrogenation reaction to obtain at relatively high temperatures, can not the process furnace that goes into operation be used, greatly reduce facility investment and process cost.Anhydrous liquid ammonia is replaced with nitrogenous distillate, namely nitrogenous benzoline is used during low temperature, by there is absorption reaction, passivation being carried out to molecular sieve, hydrogenation reaction also occurring simultaneously and obtains ammonia passivation further, and can carry out because of hydrogenation reaction the thermal source that generator heats up; Nitrogenous heavy distillate is introduced during high temperature, like this when adsorb benzoline in nitride generation desorption time again increase the stronger nitride of adsorptive power, thus guarantee to keep suppressing further molecular sieve initial activity, and some nitride reacts generation ammonia, strengthen and the initial activity of molecular sieve is suppressed.When temperature exceedes certain and swap-in stock oil, utilize Hydrogenation and cracking performance by the nitride of absorption and ammonia desorption, when after swap-in stock oil, suppressed the initial activity of hydrocracking catalyst by the nitrogen hydrogenation reaction generation ammonia improved in temperature and stock oil, thus realize the smooth transition of start-up process.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of hydroeracking unit wet method start-up method, under the prerequisite not using process furnace, implement device steadily goes into operation operation.
Hydroeracking unit wet method start-up method of the present invention comprises the steps:
Sulfurized hydrogenation cracking catalyst selected by a catalyzer that () hydroeracking unit uses;
B () will go into operation after activation oil mixes with recycle hydrogen and introduce reactive system, utilize low-temperature heat source by oily for the activation that the goes into operation temperature being warmed up to sulfide type catalyst priming reaction and starting;
C () stops using low-temperature heat source, utilize catalyst activation to react the reaction heat produced and continue to be warmed up to 180 ± 15 DEG C, then introduce the gas being rich in alkene of suitable proportion;
D () utilizes the heat of olefin hydrogenation to continue to be warmed up to 230 ± 15 DEG C, constant temperature is no less than 4 hours;
Introduce nitrogenous benzoline when () is warming up to 245 ± 15 DEG C e, when continuing to be warming up to 290 ± 15 DEG C, nitrogenous benzoline is changed to nitrogenous heavy distillate;
When () continues to be warming up to 320 ± 15 DEG C or higher temperature f, the oil that goes into operation, the light ends oil being rich in alkene and nitrogenous heavy distillate are replaced by stock oil gradually, utilize the reaction heat continuation intensification of stock oil hydrogenating desulfurization, aromatic saturation generation, by adjusting cold hydrogen amount and heat-exchange temperature adjusts reaction zone temperature in during the temperature that achieves the goal, proceed to normal production operation.Described higher temperature is generally no more than 360 DEG C.
In the inventive method step (a), said sulfurized hydrogenation catalyst, preferably to contain the sulfide type catalyst that elemental sulfur is vulcanizing agent, sulfide type catalyst can adopt the prior art of this area routine to prepare, or adopts commodity sulfide type catalyst.
In the inventive method step (a), said hydrogenation catalyst is at least containing hydrocracking catalyst, and the molecular sieve type of this catalyzer mainly comprises one or more that Y zeolite, Beta type molecular sieve, ZSM Series Molecules sieve, MCM Series Molecules sieve or complex type molecular sieve etc. are widely used in the molecular sieve of hydrogen addition technology.Hydrocracking catalyst can be prepared by the existing method in this area, also can commodity in use hydrocracking catalyst.Reaction mass, by before hydrocracking catalyst, generally needs, by Hydrobon catalyst (or hydrotreating catalyst), to carry out the reactions such as desulfurization removing nitric.
In the inventive method step (b), recycle hydrogen is the high pressure gas being rich in hydrogen in start-up process, and hydrogen purity is not less than 50%(volume), be preferably not less than 60%(volume), be preferably not less than 70%(volume).
In the inventive method step (b), the activation oil that goes into operation used when hydrogenation 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 boat coal, the diesel oil obtained through deep hydrofinishing, or boat coal, diesel oil etc. that hydrocracking obtains, the requirement nitrogen content in oil that goes into operation is not more than 200 μ g/g, is preferably not more than 100 μ g/g.The reactor inlet temperature introduced when going into operation activation oil is 50 DEG C ~ 150 DEG C.Start-up process carries out in presence of hydrogen.In start-up process, hydrogen to oil volume ratio is generally 100:1 ~ 2000:1.In start-up process, during liquid, body air speed is generally 0.1 ~ 10h
-1.The activation oil that goes into operation partly or entirely recycles, and preferably adopts hot oiling mode, and the activation oil that goes into operation of namely discharging from reactor carries out gas-liquid separation without cooling, and liquid phase circulation uses, and recycles after gas phase cooling through circulating hydrogen compressor.
In the inventive method step (b), low-temperature heat source is often referred to temperature lower than the thermal source of 240 DEG C, preferably lower than the thermal source of 200 DEG C, can be obtained by equipment such as the process furnace of interchanger, vapour generator, separation column.The temperature utilizing low-temperature heat source the oil that goes into operation to be warmed up to sulfide type catalyst priming reaction to start, refers to that sulfide type catalyst carries out activating the beginning temperature of thermopositive reaction, is generally 130 ~ 170 DEG C.
In the inventive method step (c), the gas being rich in alkene refer generally to containing monoolefine mass content be 5% ~ 80% gas hydro carbons, as the gas being rich in alkene that catalytic unit, ethylene unit, Methanol obtain for olefin hydrocarbon apparatus etc., or coke-oven gas etc., generally containing C
2~ C
4alkene.Should purifying treatment be carried out and reach the content requirement of foreign gas before entering hydrogenation unit.At this temperature, the heat release of alkene generation hydrogenation reaction, lifting gear temperature, the light ends oil introducing different ratios is needed according to the speed heated up, in general, the introduction volume being rich in olefin gas accounts for more than 20% of new hydrogen (i.e. the hydrogen make-up of start-up process) volume, is preferably 25% ~ 90%.Olefin-containing gas introduction volume is generally 5 ~ 40 DEG C by control first beds temperature in and last beds temperature out difference, is preferably 8 ~ 25 DEG C.When olefin-containing gas introduction volume is large, exothermic heat of reaction is many, and reaction temperature rising is large, quick heating.
In the inventive method step (d), constant temperature time is preferably 6 ~ 12 hours.
In the inventive method step (e), said nitrogenous benzoline refers to do and is not more than 320 DEG C, is preferably not more than the distillate of 300 DEG C, and nitrogen content is not less than 200 μ g/g usually, is preferably not less than 400 μ g/g.Nitrogen content is not more than 1000 μ g/g usually, is preferably not more than 800 μ g/g.As boat coal cut or the solar oil cut of straight run naphthenic base oil, coking boat coal cut or solar oil cut, the light ends wet goods of coal tar light ends oil, coal direct liquefaction oil.
In the inventive method step (e), said nitrogenous heavy distillate refers to any distillate of cut scope in 220 ~ 400 DEG C, any distillate preferably in 230 ~ 380 DEG C, nitrogen content is for being not less than 600 μ g/g, preferably be not less than 800 μ g/g, upper limit of nitrogen content can not need restriction, generally can at 8000 below μ g/g.Nitrogenous heavy distillate as the diesel oil distillate of straight run naphthenic base oil, fraction of coker gas oil, the diesel oil distillate of coal tar, the diesel oil distillate wet goods of coal direct liquefaction oil.
In the inventive method step (e), nitrogenous benzoline accounts for 10% ~ 50%, preferably 15% ~ 35% of the activation weight of oil that goes into operation by weight.In start-up process, the weight introducing nitrogenous benzoline accounts for 0.5% ~ 10% of hydrocracking catalyst gross weight in total nitrogen content in the nitrogenous benzoline introduced.
In the inventive method step (e), nitrogenous heavy distillate accounts for 15% ~ 80% of the activation weight of oil that goes into operation by weight, is preferably 20% ~ 40%.In general, the gross weight of nitrogenous heavy distillate is introduced with the nitrogenous benzoline gross weight many 30% ~ 60% than introducing.
In the inventive method step (f), 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 specifically can respectively according to 25% stock oil (be 25 quality % in charging be stock oil, 75 quality % be the oil that goes into operation, 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.Adjustment temperature of reaction reaches the requirement of product, last swap-in 100% stock oil.For hydrocracking process, stock oil is generally heavy distillate, as poor-quality diesel-oil by cut fraction oil, and vacuum distillate, diasphaltene wet goods.Stock oil accounts for combined feed total feed quality more than 30%, when being preferably more than 50%, stops passing into nitrogenous heavy distillate.
In the inventive method, the pressure of the reactivation process that goes into operation 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.
Embodiment
Method of the present invention is specific as follows: straight-run diesel oil is that activation goes into operation oil, first the reaction zone of activation oil by the sulfurized hydrogenation catalyst containing molecular sieve that go into operation is introduced when low temperature, then heated up by interchanger, when temperature reaches 150 DEG C, sulfide type catalyst reaction heat continues temperature to be raised to 175 DEG C ~ 185 DEG C, introduction volume accounts for new hydrogen amount 70%(volume) the purifying and catalyzing gas (mixture of catalysis drying gas and liquefied gas, alkene volume content is more than 30%), then the reaction heat utilizing hydrogenation of olefins to obtain heats up, when temperature reaches 230 DEG C, constant temperature activates 8 hours, then continue to be warming up to 240 DEG C of nitrogenous benzolines, continue to be warming up to 290 DEG C and nitrogenous benzoline is changed to nitrogenous heavy distillate, continue to be warming up to 315 DEG C, substep swap-in stock oil, temperature in is raised to temperature of reaction by the reaction heat utilizing hydrogenation reaction in stock oil to obtain, adjustment operational condition proceeds to normal production.
Particular case of the present invention is further illustrated below by embodiment.Catalyzer FF-46 is the hydrogenation pretreatment catalyst of China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute's development and production, catalyzer FC-50 and FC-32 is the hydrocracking catalyst of China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute's development and production, containing Y zeolite in FC-50 and FC-32 catalyzer.
The main composition of table 1 gas
| Unstripped gas | Purifying and catalytic cracking gas |
| Composition, v% | |
| H 2 | 2.4 |
| C 2H 4 | 6.5 |
| C 3H 6 | 24.6 |
| H 2S | 2.0 |
| CO+CO 2 | <20μg/g |
Table 2 go into operation oil and stock oil main character
| Stock oil | Straight-run diesel oil | Nitrogenous benzoline | Nitrogenous heavy distillate | Iran VGO |
| Density (20 DEG C)/gcm -3 | 0.846 | 0.786 | 0.867 | 0.914 |
| Boiling range/DEG C | 170~350 | 180~245 | 230~360 | 350~545 |
| Sulphur content, wt% | 1.0 | 0.87 | 0.96 | 1.74 |
| Nitrogen content/μ gg -1 | 80 | 750 | 2100 | 1535 |
| Aromatic hydrocarbons, wt% | 20.1 | — | — | 43.8 |
| Alkene, wt% | — | — | — | — |
Table 3 embodiment processing condition and test-results
| Processing condition | Embodiment 1 | Reference example 1 | Embodiment 2 | Embodiment 3 |
| Catalyzer | FF-46/FC-32 | FF-46/FC-32 | FF-46/FC-32 | FF-46/FC-50 |
| Start-up method | Wet method | Wet method | Wet method | Wet method |
| With or without the process furnace that goes into operation | Nothing | Have | Nothing | Nothing |
| Pressure/MPa | 15.0 | 15.0 | 12.0 | 17.0 |
| Introducing go into operation activation oil temperature/DEG C | 80 | 80 | 70 | 90 |
| Introducing purifying and catalyzing gas temperature/DEG C | 180 | — | 175 | 185 |
| Introduce nitrogenous benzoline (or anhydrous liquid ammonia) temperature/DEG C | 240 | 240(liquefied ammonia) | 240 | 240 |
| Nitrogenous benzoline introduction volume (accounting for activation to go into operation oil ratio example, %) | 20 | — | 25 | 15 |
| Change to nitrogenous heavy distillate temperature/DEG C | 290 | — | 290 | 290 |
| Stopping purifying and catalyzing gas temperature/DEG C | 290 | — | 295 | 300 |
| Nitrogenous heavy distillate introduction volume (accounting for activation to go into operation oil ratio example, %) | 20 | — | 35 | 15 |
| Change to stock oil temperature/DEG C | 315 | 315 | 315 | 315 |
| Stop nitrogenous heavy distillate (or anhydrous liquid ammonia) temperature/DEG C | 320 | 320(anhydrous liquid ammonia) | 315 | 310 |
| Catalyst activity appreciation condition and result | ||||
| Stock oil | Iran VGO | Iran VGO | Iran VGO | Iran VGO |
| Reaction pressure/MPa | 15.0 | 15.0 | 12.0 | 17.0 |
| Pretreatment section operational condition | ||||
| Catalyzer | FF-46 | FF-46 | FF-46 | FF-46 |
| Volume space velocity/h -1 | 0.9 | 0.9 | 1.1 | 1.5 |
| Hydrogen to oil volume ratio | 600 | 600 | 1000 | 1200 |
| Average reaction temperature/DEG C | 368 | 368 | 375 | 380 |
| Generate oily nitrogen content/μ gg -1 | 3.2 | 3.4 | 7.5 | 10.0 |
| Cracking zone operational condition | ||||
| Catalyzer | FC-32 | FC-32 | FC-32 | FC-50 |
| Volume space velocity/h -1 | 1.5 | 1.5 | 1.2 | 2.0 |
| Hydrogen to oil volume ratio | 1000 | 1000 | 1200 | 800 |
| Average reaction temperature/DEG C | 375 | 375 | 370 | 390 |
| Transformation efficiency, quality % | ~70 | ~70 | ~60 | ~73 |
As can be seen from embodiment, adopt the wet method start-up method of the inventive method, replace anhydrous liquid ammonia with nitrogenous distillate, not only effectively can play the activity of catalyzer, and can realize stablizing start-up process under the prerequisite not having process furnace.
Claims (35)
1. a hydroeracking unit wet method start-up method, is characterized in that comprising the steps:
Sulfurized hydrogenation cracking catalyst selected by a catalyzer that () hydroeracking unit uses;
B () will go into operation after activation oil mixes with recycle hydrogen and introduce reactive system, utilize low-temperature heat source by oily for the activation that the goes into operation temperature being warmed up to sulfide type catalyst priming reaction and starting;
C () stops using low-temperature heat source, utilize catalyst activation to react the reaction heat produced and continue to be warmed up to 180 ± 15 DEG C, then introduce the gas being rich in alkene of suitable proportion;
D () utilizes the heat of olefin hydrogenation to continue to be warmed up to 230 ± 15 DEG C, constant temperature is no less than 4 hours;
Introduce nitrogenous benzoline when () is warming up to 245 ± 15 DEG C e, when continuing to be warming up to 290 ± 15 DEG C, nitrogenous benzoline is changed to nitrogenous heavy distillate;
When () continues to be warming up to 320 ± 15 DEG C or higher temperature f, the oil that goes into operation, the gas being rich in alkene and nitrogenous heavy distillate are replaced by stock oil gradually, utilize the reaction heat continuation intensification of stock oil hydrogenating desulfurization, aromatic saturation generation, by adjusting cold hydrogen amount and heat-exchange temperature adjusts reaction zone temperature in during the temperature that achieves the goal, proceed to normal production operation;
In step (e), benzoline refers to the distillate done and be not more than 320 DEG C, and heavy distillate refers to any distillate of cut scope in 220 ~ 400 DEG C.
2. method according to claim 1, is characterized in that: in step (a), and sulfurized hydrogenation cracking catalyst is to contain the sulfide type catalyst that elemental sulfur is vulcanizing agent.
3. method according to claim 1, it is characterized in that: in step (a), hydrocracking catalyst, its molecular sieve comprises one or more in Y zeolite, Beta type molecular sieve, ZSM Series Molecules sieve, MCM Series Molecules sieve or complex type molecular sieve.
4. method according to claim 1, is characterized in that: in step (b), and recycle hydrogen is the high pressure gas being rich in hydrogen in start-up process, and hydrogen volume purity is not less than 50%.
5. method according to claim 1, is characterized in that: in step (b), and recycle hydrogen is the high pressure gas being rich in hydrogen in start-up process, and hydrogen volume purity is not less than 60%.
6. method according to claim 1, is characterized in that: in step (b), and recycle hydrogen is the high pressure gas being rich in hydrogen in start-up process, and hydrogen volume purity is not less than 70%.
7. method according to claim 1, it is characterized in that: in step (b), the activation oil that goes into operation used when hydrogenation unit goes into operation is the petroleum fractions being rich in stable hydrocarbon, the requirement nitrogen content in oil that goes into operation is not more than 200 μ g/g, and the reactor inlet temperature introduced when going into operation activation oil is 50 DEG C ~ 150 DEG C.
8. method according to claim 7, is characterized in that: in step (b), and the activation oil that goes into operation used when hydrogenation unit goes into operation is the petroleum fractions being rich in stable hydrocarbon, and the requirement nitrogen content in oil that goes into operation is not more than 100 μ g/g.
9. the method according to claim 7 or 8, is characterized in that: the activation oil that goes into operation to navigate boat coal that coal, straight-run diesel oil, the boat coal obtained through deep hydrofinishing, the diesel oil obtained through deep hydrofinishing, hydrocracking obtain or the diesel oil that hydrocracking obtains for straight run.
10. method according to claim 1, is characterized in that: start-up process carries out in presence of hydrogen, and hydrogen to oil volume ratio is 100:1 ~ 2000:1, and in start-up process, during liquid, volume space velocity is 0.1 ~ 10h
-1.
11. methods according to claim 1, is characterized in that: in step (b), and low-temperature heat source refers to that temperature is lower than the thermal source of 240 DEG C, is obtained by the furnace apparatus of interchanger, vapour generator, separation column.
12. methods according to claim 1, is characterized in that: in step (b), and low-temperature heat source refers to that temperature is lower than the thermal source of 200 DEG C.
13. methods according to claim 1, it is characterized in that: in step (b), utilize low-temperature heat source by oily for the activation that the goes into operation temperature being warmed up to sulfide type catalyst priming reaction and starting, the beginning temperature of thermopositive reaction when referring to that sulfide type catalyst activates is 130 ~ 170 DEG C.
14. methods according to claim 1, is characterized in that: in step (c), the gas being rich in alkene refer to containing monoolefine mass content be 5% ~ 80% gas hydro carbons.
15. methods according to claim 14, is characterized in that: the gas amount of quoting being rich in alkene needs to determine according to the speed heated up.
16. methods according to claim 1 or 15, is characterized in that: the introduction volume being rich in olefin gas accounts for more than 20% of new hydrogen volume amount.
17. methods according to claim 1 or 15, is characterized in that: the introduction volume being rich in olefin gas accounts for 25% ~ 90% of new hydrogen volume amount.
18. methods according to claim 16, is characterized in that: the introduction volume being rich in olefin gas, be 5 ~ 40 DEG C control by control first beds temperature in and last beds temperature out difference.
19. methods according to claim 16, is characterized in that: the introduction volume being rich in olefin gas, be 8 ~ 25 DEG C control by control first beds temperature in and last beds temperature out difference.
20. methods according to claim 1, is characterized in that: in step (e), nitrogenous benzoline refers to the distillate done and be not more than 320 DEG C, and nitrogen content is not less than 200 μ g/g.
21. methods according to claim 1, is characterized in that: in step (e), nitrogenous benzoline refers to the distillate done and be not more than 300 DEG C, and nitrogen content is not less than 400 μ g/g.
22. methods according to claim 1,20 or 21, it is characterized in that: in step (e), nitrogenous benzoline nitrogen content is not more than 1000 μ g/g usually.
23. methods according to claim 1,20 or 21, it is characterized in that: in step (e), nitrogenous benzoline nitrogen content is not more than 800 μ g/g usually.
24. methods according to claim 1,20 or 21, is characterized in that: in step (e), and nitrogenous benzoline accounts for 10% ~ 50% of the activation weight of oil that goes into operation by weight.
25. methods according to claim 1,20 or 21, is characterized in that: in step (e), and nitrogenous benzoline accounts for 15% ~ 35% of the activation weight of oil that goes into operation by weight.
26. methods according to claim 1,20 or 21, is characterized in that: in step (e), and the weight introducing nitrogenous benzoline accounts for 0.5% ~ 10% of sulfurized hydrogenation cracking catalyst gross weight in total nitrogen content in the nitrogenous benzoline introduced.
27. methods according to claim 1, is characterized in that: in step (e), and nitrogenous heavy distillate refers to any distillate of cut scope in 220 ~ 400 DEG C, and nitrogen content is for being not less than 600 μ g/g.
28. methods according to claim 1, is characterized in that: in step (e), and nitrogenous heavy distillate refers to any distillate of cut scope in 230 ~ 380 DEG C, and nitrogen content is for being not less than 800 μ g/g.
29. methods according to claim 1 or 26, is characterized in that: in step (e), and nitrogenous benzoline accounts for 10% ~ 50% of the activation weight of oil that goes into operation by weight.
30. methods according to claim 1 or 25, is characterized in that: in step (e), and nitrogenous benzoline accounts for 15% ~ 35% of the activation weight of oil that goes into operation by weight.
31. methods according to claim 27 or 28, is characterized in that: in step (e), and the gross weight introducing nitrogenous heavy distillate is with than the nitrogenous benzoline gross weight many 30% ~ 60% introduced.
32. methods according to claim 1, is characterized in that: in step (f), after sulfidation terminates, divide and progressively increase reactor feed Raw oil ratio example swap-in stock oil for 2 ~ 6 times.
33. methods according to claim 1, is characterized in that: in step (f), temperature reach 290 ± 15 DEG C or above time, stop inject be rich in alkene light ends oil.
34. methods according to claim 1, is characterized in that: the pressure of reactivation process is 50% ~ 100% of design operation pressure.
35. methods according to claim 1, is characterized in that: the pressure of reactivation process is 75% ~ 100% of design operation pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210432669.9A CN103789007B (en) | 2012-11-03 | 2012-11-03 | Wet starting method of hydrocracking unit |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210432669.9A CN103789007B (en) | 2012-11-03 | 2012-11-03 | Wet starting method of hydrocracking unit |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103789007A CN103789007A (en) | 2014-05-14 |
| CN103789007B true CN103789007B (en) | 2015-05-13 |
Family
ID=50665071
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210432669.9A Active CN103789007B (en) | 2012-11-03 | 2012-11-03 | Wet starting method of hydrocracking unit |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103789007B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106031856B (en) * | 2015-03-19 | 2018-10-09 | 上海宝钢化工有限公司 | In-situ activation method for hydrogenation reactor catalyst after ex-situ vulcanization |
| CN107304370A (en) * | 2016-04-22 | 2017-10-31 | 中国石油化工股份有限公司 | A kind of recapitalization generating oil hydrogenation process |
| CN107304369B (en) * | 2016-04-22 | 2019-11-15 | 中国石油化工股份有限公司 | A kind of recapitalization generating oil hydrogenation method |
| CN107304376B (en) * | 2016-04-22 | 2019-10-15 | 中国石油化工股份有限公司 | A kind of reformed oil liquid-phase hydrogenatin processing method |
| CN107304372B (en) * | 2016-04-22 | 2019-11-15 | 中国石油化工股份有限公司 | A kind of reformed oil liquid-phase hydrogenatin processing method |
| CN107304371B (en) * | 2016-04-22 | 2019-11-15 | 中国石油化工股份有限公司 | A kind of recapitalization generating oil hydrogenation processing method |
| CN109777472B (en) * | 2017-11-14 | 2021-07-09 | 中国石油化工股份有限公司 | Hydrogenation start-up method |
| CN108728159B (en) * | 2018-06-04 | 2020-08-25 | 上海河图工程股份有限公司 | Method for starting hydrogenation device of heavy oil slurry bed |
| CN112267098B (en) * | 2020-09-07 | 2022-03-08 | 中国科学院上海光学精密机械研究所 | Preparation method of space laser film |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4104152A (en) * | 1976-08-23 | 1978-08-01 | Uop Inc. | Hydrogenation process with sulfided catalyst |
| RU94038830A (en) * | 1994-10-19 | 1996-09-10 | С.Л. Мунд | Method for production of low-sulfur oil fractions and products |
| CN101067095A (en) * | 2006-09-09 | 2007-11-07 | 何巨堂 | Method of recovering heat in hydrocarbon hydrogenating conversion process |
| CN102051204A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Work starting method for hydrogenation process |
| CN102311766A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Class II active center hydrogenation catalyst start-up vulcanization method |
| CN102443426A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Start-up activation method for hydrogenation cracking process |
| CN102465008A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Sulfuration method of catalyst for hydrocracking technology |
-
2012
- 2012-11-03 CN CN201210432669.9A patent/CN103789007B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4104152A (en) * | 1976-08-23 | 1978-08-01 | Uop Inc. | Hydrogenation process with sulfided catalyst |
| RU94038830A (en) * | 1994-10-19 | 1996-09-10 | С.Л. Мунд | Method for production of low-sulfur oil fractions and products |
| CN101067095A (en) * | 2006-09-09 | 2007-11-07 | 何巨堂 | Method of recovering heat in hydrocarbon hydrogenating conversion process |
| CN102051204A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Work starting method for hydrogenation process |
| CN102311766A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Class II active center hydrogenation catalyst start-up vulcanization method |
| CN102443426A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Start-up activation method for hydrogenation cracking process |
| CN102465008A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Sulfuration method of catalyst for hydrocracking technology |
Non-Patent Citations (2)
| Title |
|---|
| 1.7Mt/a馏分油加氢装置开工过程探讨;牟银钢等;《当代化工》;20101231;第39卷(第06期);671-674 * |
| 2.60 Mt/a加氢精制装置开工及运行总结;郑友等;《齐鲁石油化工》;20081231;第36卷(第01期);21-27 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103789007A (en) | 2014-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103789007B (en) | Wet starting method of hydrocracking unit | |
| US9725661B2 (en) | Upgrading raw shale-derived crude oils to hydrocarbon distillate fuels | |
| CN102051205B (en) | In-situ presulfurization method of hydrogenation catalyst | |
| CN103789008B (en) | Starting method of hydrocracking unit | |
| CN104611019B (en) | A kind of low energy consumption method for hydrogen cracking producing high-quality jet fuel | |
| CN102465018B (en) | Technological method for hydrogenation of coker full-range distillate | |
| TW201247861A (en) | Hydroprocessing process using uneven catalyst volume distribution among catalyst beds in liquid-full reactors | |
| CN103789009B (en) | Wet starting method of hydrocracking unit | |
| CN110653007A (en) | Hydrogenation catalyst start-up vulcanization method | |
| CN103805235B (en) | Wet-process starting method of hydrogenation device, low-energy-consumption hydrogenation technology and hydrogenation equipment | |
| JPH0959652A (en) | Production of fuel oil base | |
| CN102311765B (en) | Startup sulfurization method for trickle bed class-II active center hydrogenation catalyst | |
| CN103789010B (en) | Wet starting method of hydrocracking unit | |
| CN102443427A (en) | Start-up vulcanizing method of hydrocracking process | |
| CN104611046B (en) | A kind of low energy consumption two-segment hydrocracking method | |
| CN103805243B (en) | A kind of method extending inferior patrol operation period of hydrogenation device | |
| CN103805253B (en) | Inferior patrol hydroprocessing process | |
| CN103789023B (en) | Hydroeracking unit start-up method | |
| CN103100449B (en) | Startup sulfuration method of liquid phase circulation hydrogenation unit | |
| CN112877090A (en) | Coal direct liquefaction circulating solvent and preparation method and system thereof | |
| CN103102929B (en) | Wet startup sulfuration method of hydrocracking unit | |
| CN103102931B (en) | Wet startup sulfuration method of hydrocracking unit | |
| CN104611026B (en) | A kind of low energy consumption produces the two-segment hydrocracking method of high-quality industrial chemicals | |
| CN103805267B (en) | A kind of hydrofinishing process of inferior patrol | |
| CN116474841A (en) | Sulfuration method of fixed bed residuum hydrogenation catalyst |
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 |