CN103059971A - Vulcanization method of catalyst used in wax oil hydrotreating process - Google Patents
Vulcanization method of catalyst used in wax oil hydrotreating process Download PDFInfo
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Abstract
The invention discloses a vulcanization method of a catalyst used in a wax oil hydrotreating process. The method comprises: (1) making a residual oil hydrotreating device or a hydrocracking device operate normally; (2) equipping a wax oil hydrotreating technological device with a hydrotreating reactor; (3) adjusting the desulfurization rate of circulating hydrogen hydrogen sulfide removal equipment in the stably operating residual oil hydrotreating device or the hydrocracking technological device; (4) introducing the hydrogen sulfide-containing gas discharged from the circulating hydrogen hydrogen sulfide removal equipment in the residual oil hydrotreating or hydrocracking technological device into a wax oil hydrotreating device, and carrying out vulcanization operations on the wax oil hydrotreating device; and (5) performing vulcanization according to normal wax oil hydrotreating device vulcanization conditions till the end. The method disclosed in the invention can improve the vulcanization efficiency and reduce vulcanizing agent consumption.
Description
Technical field
The present invention relates to a kind of wax oil hydrogenation treatment process catalyst vulcanization method, particularly comprise the Residue Hydrotreating Technology device for oil refining enterprise, the wax oil hydrogenation treatment process vulcanization process of high-pressure hydrocracking process unit and wax oil hydrogenation treatment process device.
Background technology
Because crude production rate increasess slowly and heaviness increasingly, and the world today constantly increases the clear gusoline demand, and quality product requires also more and more stricter.The petroleum fractions hydrogen addition technology is the major technique of current production clear gusoline, and wherein the technology of preparing of hydrogenation catalyst is the key of hydrogen addition technology.The active metal component of the hydrogenation catalyst of preparation is oxidation state, and oxidized catalyst is before industrial application, and its reactive metal need be converted into sulphided state and just have higher catalytic activity.Therefore, the sulfuration of catalyzer has material impact to the performance of catalyzer, is the important process step before catalyzer is used.
The method for pre-sulphuration of catalyzer can be divided into prevulcanized and the outer prevulcanized of device in the device by the mode of carrying sulphur.Up to now, both at home and abroad most refinery still adopts prevulcanized mode in the device, and namely fresh or regenerated catalyst loads and introduces vulcanizing agent behind the reactor and vulcanize, and perhaps load vulcanizing agent in catalyzer carries out vulcanization reaction in reactor.State according to vulcanizing agent is different, and the prevulcanized mode can be divided into again wet method sulfuration and dry method sulfuration in the device.The wet method sulfuration also claims the liquid phase sulfuration, is in the presence of hydrogen, the liquid curing agent is dissolved in forming vulcanized oil in the benzoline first, and then interior the contact with hydrogenation catalyst of input reactor carried out vulcanization reaction.Dry method sulfuration also claims the gas phase sulfuration, refers to catalyzer in the presence of hydrogen, directly contacts with certain density vulcanizing agent and vulcanizes.
USP4725571 discloses a kind of method of catalyst wet sulfuration, and the method adds two kinds of vulcanizing agents by adopting in vulcanized oil, finish the prevulcanized of catalyzer.
CN1362493A discloses a kind of vulcanization process of catalyst for hydroprocessing of heavy oil, at first solid-state inorganic sulphide and Hydrodemetalation catalyst are mixed, then by adopting the means that dry method sulfuration under the low temperature is combined with wet method vulcanization process under the high temperature, reduced the consumption of vulcanized oil, reduced the sulfuration cost, and the vulcanizing agent sulfurization rate is good, has given full play to the performance of catalyzer.
CN101003749A provides a kind of and has adopted 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.With the oxidation state hydrocracking catalyst reactor of packing into; Reach the air in the reactor line in the logical nitrogen replacement reactor, the reactive system adherence pressure is to the required pressure of hydrocracking reaction; Switch hydrogen behind the steady air current, the temperature that promotes again beds after hydrogen flowing quantity is stable is to required catalyst reduction temperature, and constant temperature is adjusted to hydrocracking reaction with bed temperature temperature required, and hydrogen is transferred to the required flow of hydrocracking reaction; Incision reacted hydrocarbon raw material.Need not to add again vulcanizing agent the catalyzer of oxidation state is carried out prevulcanized, avoid the problem brought by prevulcanized, and the catalyzer of partial reduction has higher hydrogenation cracking activity.
CN99123716.1 discloses again start-up method of a kind of reformer that loads two/multimetallic catalyst, comprise and use the nitrogen purging reaction unit, then at 350～420 ℃ of lower dry catalysts, pass into stock oil afterwards in reforming reactor, the control water chloride balance is until reach the operational condition of normal production.
CN01106022.0 discloses a kind of vulcanization process of catalyst for hydroprocessing of heavy oil, be characterized in solid-state inorganic sulphide and Hydrodemetalation catalyst are mixed, then by adopting the means that dry method sulfuration under the low temperature is combined with wet method vulcanization process under the high temperature, reduced the consumption of vulcanized oil, reduced the sulfuration cost, and the vulcanizing agent sulfurization rate is good, has given full play to the performance of catalyzer.
In the modern oil refining enterprise, generally comprise many cover hydrogenation units, generally comprise that wax oil hydrogenation processing, hydrocracking, residual hydrocracking, diesel oil hydrofining, gasoline hydrogenation modifying, kerosene hydrogenation are refining, hydrorefining basic oil lubricating oil, hydrorefining paraffin wax etc., and for large-scale oil refining enterprise, the hydrogenation unit of a certain type generally also comprises many covers, and hydrogenation unit has become the maximum processing unit (plant) of quantity in the oil refining enterprise.Though the purpose of different hydrogenation units is different, but desulphurization reaction is the common reaction that exists in numerous hydrogenation units, development along with the high sulfuration of raw material, and the requirement of the low sulfuration of clean fuel, desulphurization reaction becomes one of critical function of hydrogenation unit, the main purpose of some hydrogenation unit is exactly hydrogenating desulfurization, such as VGO, residual hydrocracking device etc.Prior art hydrogenation catalyst sulfidation does not have to consider the combine operations of many cover hydrogenation units only for a certain cover hydrogenation unit.
Summary of the invention
For the deficiencies in the prior art, the invention provides the vulcanization process of the applied catalyzer of a kind of wax oil hydrogenation treatment process, carry out catalyst vulcanization in conjunction with residual hydrocracking device or hydrocracking process device and go into operation, improve sulfuration efficient, reduce vulcanizing agent consumption.
The catalyst vulcanization method of wax oil hydrogenation treatment process of the present invention comprises following content:
(1) residual hydrocracking device or hydrocracking process unit normal run;
(2) wax oil hydrogenation treatment process device comprises the wax oil hydrogenation treatment reactor, and reactor charge oxidation state wax oil hydrogenation is processed catalyzer;
(3) wax oil hydrogenation treatment process device carries out the operations such as gas displacement, catalyzer is dry, device is airtight;
(4) desulfurization degree of recycle hydrogen de sulfuration hydrogen production device in the residual hydrocracking device of adjustment steady running or the hydroeracking unit;
The H 2 S-containing gas of (5) the recycle hydrogen de sulfuration hydrogen production device of residual hydrocracking device or hydroeracking unit being discharged is introduced VGO, and VGO is carried out vulcanisation operation;
(6) adding wax oil hydrogenation processes the sulfidation of catalyzer and comprises: at 200 ℃ ~ 240 ℃ lower constant temperature 4h ~ 16h, H
2The concentration of S is controlled to be 500 μ L/L ~ 1000 μ L/L; At 260 ℃ ~ 300 ℃ lower constant temperature 2h ~ 16h hours, H
2The concentration of S is controlled to be 3000 μ L/L ~ 20000 μ L/L; At 310 ℃ ~ 380 ℃ lower constant temperature 4h ~ 20h, H
2The concentration of S is at 5000 μ L/L ~ 20000 μ L/L, and sulfuration finishes;
(7) after sulfuration finished, VGO carried out self recycle hydrogen cyclical operation, adjusted bed to temperature of reaction, switched stock oil and carried out the hydrotreatment reaction.
In the inventive method, residual hydrocracking device or the hydroeracking unit of the described steady running of step (1) generally are the high-tension units of stably manufactured running in the oil refining enterprise, and pressure rating is identical with VGO, is generally 10 ~ 25MPa.The operational condition of residual hydrocracking device or hydroeracking unit is undertaken by normal running, the desulfurization degree of the concentration controlled circulation hydrogen depriving hydrogen sulphide device of required hydrogen sulfide in the time of only need going into operation sulfuration by VGO.
In the inventive method, the described VGO of step (2) generally comprises wax oil hydrogenation processing reaction system.
In the inventive method, step (2) wax oil hydrogenation is processed catalyzer generally take the refractory porous oxide as carrier, such as the composite oxides of aluminum oxide, silicon oxide, amorphous silicon aluminium, titanium oxide, molecular sieve and several elements or mixed oxide carrier etc.It is carrier that wax oil hydrogenation is processed the no acidic or weakly acidic material of catalyzer normal operation, such as aluminum oxide, silicon oxide, amorphous silicon aluminium etc., load hydrogenation active metals component.The hydrogenation activity component of wax oil hydrogenation processing catalyzer is one or more among W, Mo, Ni and the Co, is generally 3wt% ~ 50wt% in oxide compound hydrogenation activity component concentration.Wax oil hydrogenation is processed catalyzer can select suitable commercial catalyst by the needs of technical process, can by existing method preparation, also can be the regenerated catalyst after the regeneration of decaying catalyst process also.
In the inventive method, the described gas displacement of step (3), device be airtight etc. to be operating as start-up method well-known to those skilled in the art.
In the inventive method, the described residual hydrocracking device of step (4) or hydroeracking unit, can regulate depriving hydrogen sulphide efficient by method well known to those skilled in the art, vulcanize needed hydrogen sulfide consumption to satisfy VGO, the general mode of regulating recycle hydrogen de sulfuration hydrogen production device absorption agent (being generally amine liquid) consumption that adopts is regulated.The feed sulphur content of residual hydrocracking device or hydroeracking unit is generally the 1%(quality) more than, be preferably 1.5% ~ 5%.
In the inventive method, the described H 2 S-containing gas that the recycle hydrogen de of residual hydrocracking device or hydrocracking process device is vulcanized hydrogen production device of step (5), introduce VGO, namely begin the machinery gas circulation, the recycle hydrogen de sulfuration hydrogen production device of VGO is opened, make hydrogen sulfide content in the gas that enters residual hydrocracking device or hydroeracking unit satisfy the requirement of wax oil residual hydrocracking device or hydroeracking unit, be generally below the 500 μ L/L.
In the inventive method, the sulfidation of described VGO can adopt wet method sulfuration or dry method sulfuration.As adopt the wet method sulfuration, and generally between 130 ℃ ~ 180 ℃, in the VGO reactive system, introduce the vulcanized oil that goes into operation, vulcanized oil absorption temperature rise ripple can vulcanize according to the described process of step (6) by behind whole beds; If adopt the dry method sulfuration, directly vulcanize according to the described process of step (6) and get final product.The sulfidation of step (6) VGO is generally as follows: during 130 ℃ ~ 180 ℃ of VGOs, stop the recycle hydrogen system of residual hydrocracking device or hydroeracking unit, adjust recycle hydrogen de sulfuration hydrogen production device desulfurization degree, the recycle hydrogen of residual hydrocracking device or hydroeracking unit is introduced wax oil hydrogenation treatment process device go into operation, and confirm H
2S penetrates wax oil hydrogenation treatment process reactor catalyst bed.Adjust afterwards the depriving hydrogen sulphide ability of the recycle hydrogen de sulfuration hydrogen production device of residual hydrocracking device or hydroeracking unit, reach the required concentration of hydrogen sulfide of VGO sulfidation, speed with 1 ℃/h ~ 30 ℃/h rises to 200 ℃ ~ 240 ℃ with each bed of wax oil hydrogenation treatment process reactor, constant temperature 4h ~ 16h hour, then the speed with 1 ℃/h ~ 30 ℃/h rises to 260 ℃ ~ 300 ℃ with each bed of hydrocracking process reactor, constant temperature 2h ~ 16h hour, speed with 1 ℃/h ~ 30 ℃/h rises to 310 ℃ ~ 380 ℃ with each bed of wax oil hydrogenation treatment process reactor, constant temperature 4h ~ 20h hour.When VGO goes into operation in the recycle hydrogen concentration of hydrogen sulfide refer to H in the circulating hydrogen in the outlet of residual hydrogenation equipment or hydroeracking unit depriving hydrogen sulphide device
2The concentration of S.
In the inventive method, after the described VGO sulfuration of step (7) finishes, adjust to normal workflow, by method adjusting operation condition well known to those skilled in the art, switch stock oil.
The inventive method is the recycle hydrogen of residual hydrocracking device or hydroeracking unit, and the vulcanization process as the vulcanisation cycle hydrogen of the Containing Sulfur agent of wax oil hydrogenation treatment process device has following advantage:
1, oxidation state wax oil hydrogenation provided by the invention is processed the vulcanization process of catalyzer, can guarantee higher cure efficiency.
2, method provided by the invention as long as existing installation is simply transformed, just can reach requirement, reduces the sulfuration investment, avoids simultaneously manually injecting vulcanizing agent to the murder by poisoning of human body, and the easy operation that goes into operation has considerable economic benefit and social benefit.
3, because in the method, employing is with the output gas of the desulfurizer of residual hydrocracking device or hydroeracking unit, introduce VGO, form the machinery gas circulation, and with the processing power of control residual hydrocracking device or hydroeracking unit recycle hydrogen de sulfuration hydrogen production device, provide wax oil hydrogenation treatment process device at the sulfidation vulcanizing agent, effectively utilize the hydrogen sulfide in the desulfurizer output gas of residual hydrocracking device or hydroeracking unit.
4, adopt the catalyst vulcanization start-up method of wax oil hydrogenation treatment process provided by the invention, its technique is simple, simple operation, and security is good, environmental friendliness, and have higher catalytic activity.
Description of drawings
Fig. 1 is wax oil hydrogenation treatment process catalyst vulcanization method flow schematic diagram of the present invention.
Wherein: 1-residual hydrocracking device, 2-residual hydrocracking device reaction product gas-liquid separator, 3-residual hydrocracking device recycle hydrogen de sulfuration hydrogen production device, the 4-VGO, 5-VGO reaction product gas-liquid separator, 6-VGO recycle hydrogen de sulfuration hydrogen production device.
Embodiment
In the inventive method, adopt the H 2 S-containing gas of the recycle hydrogen de sulfuration hydrogen production device of residual hydrocracking device or hydroeracking unit, introduce VGO, it is the machinery gas circulation, the recycle hydrogen de of VGO sulfuration hydrogen production device is opened, and control enters the requirement that hydrogen sulfide content in the gas of residual hydrocracking device or hydroeracking unit satisfies residual hydrocracking device or hydroeracking unit.When reaction bed temperature reaches 95 ~ 180 ℃, can introduce or do not introduce vulcanized oil, the H 2 S-containing gas that draws the recycle hydrogen de sulfuration hydrogen production device of residual hydrocracking device or hydroeracking unit enters reactor, and the vulcanized oil volume space velocity is 0.5 ~ 5h
-1, hydrogen to oil volume ratio is 100 ~ 1500.
Further specify concrete grammar of the present invention and effect below in conjunction with accompanying drawing.
As shown in Figure 1, in the catalyst vulcanization process of VGO, after circulating hydrogen and residual oil raw material mix, process residual hydrocracking device 1(is take the residual hydrocracking device as example), enter residual hydrocracking device reaction product gas-liquid separator 2, carry out gas and generate separating of oil, gas is through residual hydrocracking device recycle hydrogen de sulfuration hydrogen production device 3, carry out a certain amount of depriving hydrogen sulphide, hydrogen sulfide containing circulating hydrogen is introduced VGO 4, vulcanize, pass through again VGO reaction product gas-liquid separator 5, enter VGO recycle hydrogen de sulfuration hydrogen production device 6, carry out depriving hydrogen sulphide and process, turn back to residual hydrocracking device 1.
Below by specific embodiment the inventive method is explained in detail.
The oxidation state hydrotreating catalyst that adopts among the embodiment among the present invention is the FF-14 of Fushun Petrochemical Research Institute's development and production.The FF-14 catalyzer is take aluminum oxide as carrier, take Mo-Ni-Co as active ingredient.Among each embodiment, the FF-14 usage quantity is 100 grams.The per-cent that does not wherein indicate benchmark is weight percentage.
Simultaneously used stock oil character sees Table that catalyst system therefor technology assessment condition sees Table 2 among 1, the embodiment in the embodiment of the invention.
Table 1 stock oil
| Stock oil | Iran VGO |
| Density (20 ℃), g.cm -3 | 0.9168 |
| Boiling range (IBP/EBP), ℃ | 336/546 |
| Carbon/hydrogen, % | 86.44/12.76 |
| Sulphur, % | 2.64 |
| Nitrogen, μ g.g -1 | 2087 |
Table 2 catalyst process appreciation condition
| Stock oil | Iran VGO |
| Catalyzer | FF-14 |
| The hydrogen dividing potential drop, MPa | 14.0 |
| Hydrogen to oil volume ratio | 600 |
| Volume space velocity, h -1 | 1.20 |
| Temperature of reaction, ℃ | 360 |
Comparative example 1
The FF-14 catalyzer is packed in the hydrotreating reactor, carries out airtight again.Airtight qualified after, the hydrogen dividing potential drop is adjusted into 14.0MPa, temperature is adjusted into 170 ℃, begins to introduce vulcanized oil, bed temperature steadily after, begin sulfuration and inject (vulcanizing agent is DMDS) behind the vulcanizing agent, hydrogen to oil volume ratio is 600.Beginning is warming up to 230 ℃ with 5 ℃/h, and after vulcanizing agent penetrates each beds constant temperature 6 hours.After finishing constant temperature, hydrogen sulfide and circulating hydrogen gas mixture continue to be warming up to 290 ℃ with 5 ℃/h, constant temperature 6 hours.Constant temperature finishes, and continues to be warming up to 320 ℃ with 4 ℃/h, constant temperature 6 hours.Constant temperature finishes, and switches stock oil by operation.Rise to 360 ℃ of runnings 48 hours after switching raw material, adopt the finished product crude oil sample analysis, catalyst activity the results are shown in Table 3.
Embodiment 1
Steady running residual oil treatment unit, after circulating hydrogen and residual oil raw material mix, through residual hydrocracking device 1, enter residual hydrocracking device reaction product gas-liquid separator 2, carry out gas and generate separating of oil, gas turns back to residual hydrocracking device 1 through residual hydrocracking device recycle hydrogen de sulfuration hydrogen production device 3.Simultaneously, the FF-14 catalyzer is packed in the hydrotreating reactor, through super-dry, carries out airtight again.Airtight qualified after, the hydrogen dividing potential drop is adjusted into 14.0 MPa, temperature is adjusted into 160 ℃, begins to introduce vulcanized oil.After bed temperature is steady, adjust residual hydrocracking device recycle hydrogen de sulfuration hydrogen production device 3, hydrogen sulfide containing circulating hydrogen is introduced VGO 4, vulcanize, pass through again VGO reaction product gas-liquid separator 5, enter VGO recycle hydrogen de sulfuration hydrogen production device 6, carry out depriving hydrogen sulphide and process, turn back to residual hydrocracking device 1.Set up the circulating hydrogen system of residual hydrocracking device and VGO associating.After flow process is got through, and confirm H
2S penetrates wax oil hydrogenation reactor catalyst bed.Adjust afterwards the depriving hydrogen sulphide ability of the recycle hydrogen de sulfuration hydrogen production device of residual hydrocracking device, reach the required concentration of hydrogen sulfide of VGO sulfidation, each bed of wax oil hydrogenation treatment reactor is risen to 230 ℃, H with the speed of 5 ℃/h
2The concentration of S is controlled to be 5000 μ L/L, constant temperature 10 hours; Then the speed with 3 ℃/h rises to 290 ℃ with each bed of wax oil hydrogenation treatment reactor, H
2The concentration of S is controlled to be 10000 μ L/L, constant temperature 10 hours; Speed with 5 ℃/h rises to 320 ℃, H with each bed of wax oil hydrogenation treatment process reactor
2The concentration of S is controlled to be 15000 μ L/L, constant temperature 10 hours.Adjust temperature of reactor, introduce stock oil.Introduce raw material afterreaction temperature and be adjusted to 360 ℃ of runnings 48 hours, adopt the finished product crude oil sample analysis, catalyst activity the results are shown in Table 3.
Embodiment 2
Steady running residual oil treatment unit, after circulating hydrogen and residual oil raw material mix, through residual hydrocracking device 1, enter residual hydrocracking device reaction product gas-liquid separator 2, carry out gas and generate separating of oil, gas turns back to residual hydrocracking device 1 through residual hydrocracking device recycle hydrogen de sulfuration hydrogen production device 3.Simultaneously, the FF-14 catalyzer is packed in the hydrotreating reactor, through super-dry, carries out airtight again.Airtight qualified after, the hydrogen dividing potential drop is adjusted into 14.0MPa, temperature is adjusted into 180 ℃.At this moment, adjust residual hydrocracking device recycle hydrogen de sulfuration hydrogen production device 3, hydrogen sulfide containing circulating hydrogen is introduced VGO 4, vulcanize, pass through again VGO reaction product gas-liquid separator 5, enter VGO recycle hydrogen de sulfuration hydrogen production device 6, carry out depriving hydrogen sulphide and process, turn back to residual hydrocracking device 1.Set up the circulating hydrogen system of residual hydrocracking device and VGO associating.After flow process is got through, and confirm H
2S penetrates wax oil hydrogenation treatment process reactor catalyst bed.Adjust afterwards the depriving hydrogen sulphide ability of the recycle hydrogen de sulfuration hydrogen production device of residual hydrocracking device, reach the required concentration of hydrogen sulfide of VGO sulfidation, with the speed of 3 ℃/h each bed of wax oil hydrogenation treatment process reactor is risen to 220 ℃, H
2The concentration of S is controlled to be 5000 μ L/L, constant temperature 12 hours; Then the speed with 3 ℃/h rises to 290 ℃, H with each bed of wax oil hydrogenation treatment process reactor
2The concentration of S is controlled to be 10000 μ L/L, constant temperature 12 hours; Speed with 3 ℃/h rises to 380 ℃, H with each bed of wax oil hydrogenation treatment process reactor
2The concentration of S is controlled to be 16000 μ L/L, constant temperature 8 hours.After sulfuration finishes, adjust temperature, introduce stock oil.Introduce raw material afterreaction temperature and be adjusted to 360 ℃ of runnings 48 hours, adopt the finished product crude oil sample analysis, catalyst activity the results are shown in Table 3.
Embodiment 3
Steady running residual oil treatment unit, after circulating hydrogen and residual oil raw material mix, through residual hydrocracking device 1, enter residual hydrocracking device reaction product gas-liquid separator 2, carry out gas and generate separating of oil, gas turns back to residual hydrocracking device 1 through residual hydrocracking device recycle hydrogen de sulfuration hydrogen production device 3.Simultaneously, FF-14 packs in the reactor, through super-dry, carries out airtight again.Airtight qualified after, the hydrogen dividing potential drop is adjusted into 14.0MPa, temperature is adjusted into 160 ℃, begins to introduce vulcanized oil.After bed temperature is steady, adjust residual hydrocracking device recycle hydrogen de sulfuration hydrogen production device 3, hydrogen sulfide containing circulating hydrogen is introduced VGO 4, vulcanize, pass through again VGO reaction product gas-liquid separator 5, enter VGO recycle hydrogen de sulfuration hydrogen production device 6, carry out depriving hydrogen sulphide and process, turn back to residual hydrocracking device 1.Set up the circulating hydrogen system of residual hydrocracking device and VGO associating.After flow process is got through, and confirm H
2S penetrates wax oil hydrogenation treatment process reactor catalyst bed.Adjust afterwards the depriving hydrogen sulphide ability of the recycle hydrogen de sulfuration hydrogen production device of residual hydrocracking device, reach the required concentration of hydrogen sulfide of VGO sulfidation, with the speed of 8 ℃/h each bed of wax oil hydrogenation treatment process reactor is risen to 220 ℃, H
2The concentration of S is controlled to be 5000 μ L/L, constant temperature 8 hours; Then the speed with 5 ℃/h rises to 290 ℃, H with each bed of wax oil hydrogenation treatment process reactor
2The concentration of S is controlled to be 10000 μ L/L, constant temperature 10 hours; Speed with 10 ℃/h rises to 320 ℃, H with each bed of wax oil hydrogenation treatment process reactor
2The concentration of S is controlled to be 15000 μ L/L, constant temperature 10 hours.Adjust temperature, introduce stock oil.Introduce raw material afterreaction temperature and be adjusted to 360 ℃ of runnings 48 hours, adopt the finished product crude oil sample analysis, catalyst activity the results are shown in Table 3.
Embodiment 4
Steady running residual oil treatment unit, after circulating hydrogen and residual oil raw material mix, through residual hydrocracking device 1, enter residual hydrocracking device reaction product gas-liquid separator 2, carry out gas and generate separating of oil, gas turns back to residual hydrocracking device 1 through residual hydrocracking device recycle hydrogen de sulfuration hydrogen production device 3.Simultaneously, the FF-14 catalyzer is packed in the hydrotreating reactor, through super-dry, carries out airtight again.Airtight qualified after, the hydrogen dividing potential drop is adjusted into 14.0MPa, temperature is adjusted into 170 ℃.At this moment, adjust residual hydrocracking device recycle hydrogen de sulfuration hydrogen production device 3, hydrogen sulfide containing circulating hydrogen is introduced VGO 4, vulcanize, pass through again VGO reaction product gas-liquid separator 5, enter VGO recycle hydrogen de sulfuration hydrogen production device 6, carry out depriving hydrogen sulphide and process, turn back to residual hydrocracking device 1.Set up the circulating hydrogen system of residual hydrocracking device and VGO associating.After flow process is got through, and confirm H
2S penetrates wax oil hydrogenation treatment process reactor catalyst bed.Adjust afterwards the depriving hydrogen sulphide ability of the recycle hydrogen de sulfuration hydrogen production device of residual hydrocracking device, reach the required concentration of hydrogen sulfide of VGO sulfidation, with the speed of 3 ℃/h each bed of wax oil hydrogenation treatment process reactor is risen to 230 ℃, H
2The concentration of S is controlled to be 5000 μ L/L, constant temperature 10 hours; Then the speed with 5 ℃/h rises to 290 ℃, H with each bed of wax oil hydrogenation treatment process reactor
2The concentration of S is controlled to be 10000 μ L/L, constant temperature 10 hours; Speed with 3 ℃/h rises to 380 ℃, H with each bed of wax oil hydrogenation treatment process reactor
2The concentration of S is controlled to be 16000 μ L/L, constant temperature 8 hours.After sulfuration finishes, adjust temperature, introduce stock oil.Introduce raw material afterreaction temperature and be adjusted to 360 ℃ of runnings 48 hours, adopt the finished product crude oil sample analysis, catalyst activity the results are shown in Table 3.
Embodiment 5
Steady running residual oil treatment unit, after circulating hydrogen and residual oil raw material mix, through residual hydrocracking device 1, enter residual hydrocracking device reaction product gas-liquid separator 2, carry out gas and generate separating of oil, gas turns back to residual hydrocracking device 1 through residual hydrocracking device recycle hydrogen de sulfuration hydrogen production device 3.Simultaneously, the FF-14 catalyzer is packed in the hydrotreating reactor, through super-dry, carries out airtight again.Airtight qualified after, the hydrogen dividing potential drop is adjusted into 14.0MPa, temperature is adjusted into 150 ℃, begins to introduce vulcanized oil.After bed temperature is steady, adjust residual hydrocracking device recycle hydrogen de sulfuration hydrogen production device 3, hydrogen sulfide containing circulating hydrogen is introduced VGO 4, vulcanize, pass through again VGO reaction product gas-liquid separator 5, enter VGO recycle hydrogen de sulfuration hydrogen production device 6, carry out depriving hydrogen sulphide and process, turn back to residual hydrocracking device 1.Set up the circulating hydrogen system of residual hydrocracking device and VGO associating.After flow process is got through, and confirm H
2S penetrates wax oil hydrogenation treatment process reactor catalyst bed.Adjust afterwards the depriving hydrogen sulphide ability of the recycle hydrogen de sulfuration hydrogen production device of residual hydrocracking device, reach the required concentration of hydrogen sulfide of VGO sulfidation, with the speed of 10 ℃/h each bed of wax oil hydrogenation treatment process reactor is risen to 230 ℃, H
2The concentration of S is controlled to be 5000 μ L/L, constant temperature 8h hour; Then the speed with 5 ℃/h rises to 290 ℃, H with each bed of wax oil hydrogenation treatment process reactor
2The concentration of S is controlled to be 10000 μ L/L, constant temperature 4 hours; Speed with 10 ℃/h rises to 320 ℃, H with each bed of wax oil hydrogenation treatment process reactor
2The concentration of S is controlled to be 15000 μ L/L, constant temperature 10 hours.Adjust temperature, introduce stock oil.Introduce raw material afterreaction temperature and be adjusted to 360 ℃ of runnings 48 hours, adopt the finished product crude oil sample analysis, catalyst activity the results are shown in Table 3.
Embodiment 6
Technical process is with reference to Fig. 1: the steady running hydroeracking unit, after circulating hydrogen and VGO raw material mix, through hydroeracking unit 1, enter hydroeracking unit reaction product gas-liquid separator 2, carry out gas and generate separating of oil, gas turns back to hydroeracking unit 1 through hydroeracking unit recycle hydrogen de sulfuration hydrogen production device 3.Simultaneously, the FF-14 catalyzer is packed in the hydrotreating reactor, through super-dry, carries out airtight again.Airtight qualified after, the hydrogen dividing potential drop is adjusted into 14.0MPa, temperature is adjusted into 160 ℃.At this moment, adjust hydroeracking unit recycle hydrogen de sulfuration hydrogen production device 3, hydrogen sulfide containing circulating hydrogen is introduced VGO 4, vulcanize, pass through again VGO reaction product gas-liquid separator 5, enter VGO recycle hydrogen de sulfuration hydrogen production device 6, carry out depriving hydrogen sulphide and process, turn back to hydroeracking unit 1.Set up the circulating hydrogen system of hydroeracking unit and VGO associating.After flow process is got through, and confirm H
2S penetrates wax oil hydrogenation treatment process reactor catalyst bed.Adjust afterwards the depriving hydrogen sulphide ability of the recycle hydrogen de sulfuration hydrogen production device of hydroeracking unit, reach the required concentration of hydrogen sulfide of VGO sulfidation, with the speed of 3 ℃/h each bed of wax oil hydrogenation treatment process reactor is risen to 210 ℃, H
2The concentration of S is controlled to be 6000 μ L/L, constant temperature 10 hours; Then the speed with 5 ℃/h rises to 300 ℃, H with each bed of wax oil hydrogenation treatment process reactor
2The concentration of S is controlled to be 10000 μ L/L, constant temperature 12 hours; Speed with 3 ℃/h rises to 370 ℃, H with each bed of wax oil hydrogenation treatment process reactor
2The concentration of S is controlled to be 16000 μ L/L, constant temperature 8 hours.After sulfuration finishes, adjust temperature, introduce stock oil.Introduce raw material afterreaction temperature and be adjusted to 360 ℃ of runnings 48 hours, adopt the finished product crude oil sample analysis, catalyst activity the results are shown in Table 3.
Table 3 wax oil hydrogenation is processed catalyst activity relatively
| The embodiment numbering | The treated oil sulphur content, μ g/g | The treated oil nitrogen content, μ g/g |
| Comparative example 1 | 368 | 98 |
| Embodiment 1 | 196 | 86 |
| Embodiment 2 | 216 | 85 |
| Embodiment 3 | 287 | 90 |
| Embodiment 4 | 308 | 87 |
| Embodiment 5 | 297 | 91 |
| Embodiment 6 | 209 | 86 |
Result by table 3 can find out, adopts sulfuration start-up method provided by the invention, and its catalyst activity also is better than conventional wax oil hydrogenation and processes the catalyst vulcanization start-up method.But because the inventive method only needs existing installation is transformed, just can reach requirement, reducing simultaneously the investment of vulcanizing plant and the purchase of vulcanizing agent uses, avoid manually injecting vulcanizing agent to the murder by poisoning of human body, the easy operation that goes into operation, and use to greatest extent the oil refining by product, considerable economic benefit and social benefit are arranged.
Claims (11)
1. the catalyst vulcanization method of a wax oil hydrogenation treatment process may further comprise the steps:
(1) residual hydrocracking device or hydrocracking process unit normal run;
(2) wax oil hydrogenation treatment process device comprises the wax oil hydrogenation treatment reactor, and reactor charge oxidation state wax oil hydrogenation is processed catalyzer;
(3) wax oil hydrogenation treatment process device carries out the operations such as gas displacement, catalyzer is dry, device is airtight;
(4) desulfurization degree of recycle hydrogen de sulfuration hydrogen production device in the residual hydrocracking device of adjustment steady running or the hydroeracking unit;
The H 2 S-containing gas of (5) the recycle hydrogen de sulfuration hydrogen production device of residual hydrocracking device or hydroeracking unit being discharged is introduced VGO, and VGO is carried out vulcanisation operation;
(6) adding wax oil hydrogenation processes the sulfidation of catalyzer and comprises: at 200 ℃ ~ 240 ℃ lower constant temperature 4h ~ 16h, H
2The concentration of S is controlled to be 500 μ L/L ~ 1000 μ L/L; At 260 ℃ ~ 300 ℃ lower constant temperature 2h ~ 16h hours, H
2The concentration of S is controlled to be 3000 μ L/L ~ 20000 μ L/L; At 310 ℃ ~ 380 ℃ lower constant temperature 4h ~ 20h, H
2The concentration of S is at 5000 μ L/L ~ 20000 μ L/L, and sulfuration finishes;
(7) after sulfuration finished, VGO carried out self recycle hydrogen cyclical operation, adjusted bed to temperature of reaction, switched stock oil and carried out the hydrotreatment reaction.
2. in accordance with the method for claim 1, it is characterized in that: the residual hydrogenation equipment of the steady running in the step (1) or hydrocracking process device, be the high-tension unit of stably manufactured running in the oil refining enterprise, pressure rating is identical with VGO, and pressure is 10 ~ 25MPa.
3. it is characterized in that in accordance with the method for claim 1: the described VGO of step (2) comprises wax oil hydrogenation processing reaction system.
4. in accordance with the method for claim 1, it is characterized in that: the feed sulfur mass content of described residual hydrocracking device or hydroeracking unit is more than 1%, to be preferably 2% ~ 5%.
5. in accordance with the method for claim 1, it is characterized in that, the sulfidation of the described VGO of step (6) adopts the wet method sulfuration, between 130 ℃ ~ 180 ℃, in the VGO reactive system, introduce the vulcanized oil that goes into operation, vulcanized oil absorption temperature rise ripple carries out follow-up warming temperature again by behind whole beds.
6. in accordance with the method for claim 1, it is characterized in that, the sulfidation of the described VGO of step (6) adopts the dry method sulfuration.
7. in accordance with the method for claim 1, it is characterized in that, the described wax oil hydrogenation of step (2) is processed catalyzer take no acidic or weakly acidic refractory porous oxide as carrier, the hydrogenation activity component is one or more among W, Mo, Ni and the Co, is generally 3wt% ~ 50wt% in oxide compound hydrogenation activity component concentration.
8. in accordance with the method for claim 1, it is characterized in that the described residual hydrocracking device of step (4) or hydroeracking unit adopt the mode of regulating recycle hydrogen de sulfuration hydrogen production device absorption agent consumption to adjust desulfurization degree.
9. in accordance with the method for claim 1, it is characterized in that: the described H 2 S-containing gas that the recycle hydrogen de of residual hydrocracking device or hydrocracking process device is vulcanized hydrogen production device of step (5), introduce VGO, namely begin the machinery gas circulation, the recycle hydrogen de of VGO sulfuration hydrogen production device is opened, and makes hydrogen sulfide content in the gas that enters residual hydrocracking device or hydroeracking unit satisfy the requirement of wax oil residual hydrocracking device or hydroeracking unit.
10. in accordance with the method for claim 1, it is characterized in that, in the sulfidation of step (6) VGO, during 130 ℃ ~ 180 ℃ of VGOs, stop the recycle hydrogen system of residual hydrocracking device or hydroeracking unit, adjust recycle hydrogen de sulfuration hydrogen production device desulfurization degree, the recycle hydrogen of residual hydrocracking device or hydroeracking unit is introduced wax oil hydrogenation treatment process device go into operation, and confirm H
2S penetrates wax oil hydrogenation treatment process reactor catalyst bed, adjusts afterwards the depriving hydrogen sulphide ability of the recycle hydrogen de sulfuration hydrogen production device of residual hydrocracking device or hydroeracking unit, reaches the required concentration of hydrogen sulfide of VGO sulfidation.
11. in accordance with the method for claim 1, it is characterized in that, the heat-up rate in the sulfidation of step (6) hydrotreater is 1 ℃/h ~ 30 ℃/h.
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