CN103059971B - 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 Residue Hydrotreating Technology device is comprised 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 clear gusoline demand, and quality product requires also more and more stricter.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 active metal need be converted into sulphided state and just have higher catalytic activity.Therefore, the performance of sulfuration to catalyzer of catalyzer has material impact, is the important process step before catalyst application.
The method for pre-sulphuration of catalyzer can be divided into in-situ presulfurization and ex situ presulfiding by the mode of carrying sulphur.Up to now, domestic and international most refinery still adopts in-situ presulfurization mode, and namely fresh or regenerated catalyst loads and after reactor, introduces vulcanizing agent carry out sulfuration, or sulfur loaded agent in the catalyst, in reactor, carry out vulcanization reaction.Different according to the state of vulcanizing agent, in-situ presulfurization mode can be divided into again wet method sulfuration and dry pre-sulfiding.Wet method sulfuration also claims liquid phase sulfuration, is in presence of hydrogen, first liquid sulfur agent is dissolved in benzoline and forms vulcanized oil, then contacts with hydrogenation catalyst in input reactor and carries out vulcanization reaction.Dry pre-sulfidingly also claim gas-phase presulfiding, refer to that catalyzer in the presence of hydrogen gas, directly with certain density sulfurizing agent and carry out sulfuration.
USP4725571 discloses a kind of method of catalyst wet sulfuration, and the method adds two kinds of vulcanizing agents by adopting in vulcanized oil, has carried out the prevulcanized of catalyzer.
CN1362493A discloses a kind of vulcanization process of catalyst for hydroprocessing of heavy oil, first solid-state inorganic sulphide is mixed with Hydrodemetalation catalyst, then by adopting the means combined with wet method vulcanization process under high temperature dry pre-sulfiding under low temperature, decrease the consumption of vulcanized oil, reduce sulfuration cost, and vulcanizing agent sulfurization rate is good, give full play to the performance of catalyzer.
CN101003749A provides a kind of under the existing hydrocracking catalyst condition of employing, without the need to carrying out the start-up method of the oxidation state hydrocracking catalyst of the prevulcanized of catalyzer.Oxidation state hydrocracking catalyst is loaded reactor; Air in logical nitrogen replacement reactor and in reactor line, pressure needed for reactive system adherence pressure to hydrocracking reaction; Switch hydrogen after steady air current, hydrogen flowing quantity promotes the temperature of beds again to required catalyst reduction temperature after stablizing, constant temperature, is adjusted to hydrocracking reaction by bed temperature temperature required, hydrogen is adjusted to flow needed for hydrocracking reaction; Incision reacted hydrocarbon raw material.Without the need to additional vulcanizing agent again, prevulcanized is carried out to the catalyzer of oxidation state, avoid the problem brought by prevulcanized, and the catalyzer of partial reduction has higher hydrogenation cracking activity.
CN99123716.1 discloses a kind of reformer start-up method again loading two/multimetallic catalyst, comprise and use nitrogen purging reaction unit, then dry catalyst at 350 ~ 420 DEG C, backward reforming reactor in pass into stock oil, control water chloride balance until reach normal operational condition of producing.
CN01106022.0 discloses a kind of vulcanization process of catalyst for hydroprocessing of heavy oil, solid-state inorganic sulphide is characterized in mix with Hydrodemetalation catalyst, then by adopting the means combined with wet method vulcanization process under high temperature dry pre-sulfiding under low temperature, decrease the consumption of vulcanized oil, reduce sulfuration cost, and vulcanizing agent sulfurization rate is good, give full play to the performance of catalyzer.
In modern oil refining enterprise, generally comprise and overlap hydrogenation unit more, generally comprise that wax oil hydrogenation process, 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 processing unit (plant) that in oil refining enterprise, quantity is maximum.Though the object of different hydrogenation unit is different, but desulphurization reaction is the common reaction existed in numerous hydrogenation unit, along with the development that raw material is high-sulfurized, and the requirement of the low sulfuration of clean fuel, one of desulphurization reaction critical function becoming hydrogenation unit, the main purpose of some hydrogenation unit is exactly hydrogenating desulfurization, as VGO, residual hydrocracking device etc.Prior art hydrogenation catalyst sulfidation, only for certain a set of hydrogenation unit, does not have the combine operations considering many cover hydrogenation units.
Summary of the invention
For the deficiencies in the prior art, the invention provides the vulcanization process of the catalyzer that a kind of wax oil hydrogenation treatment process is applied, carry out catalyst vulcanization in conjunction with residual hydrocracking device or hydrocracking process device to go into operation, improve curing efficiency, 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 wax oil hydrogenation treatment reactor, reactor charge oxidation state wax oil hydrogenation process 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 steady running or hydroeracking unit is adjusted;
(5) by the H 2 S-containing gas that the recycle hydrogen de sulfuration hydrogen production device of residual hydrocracking device or hydroeracking unit is discharged, introduce VGO, vulcanisation operation is carried out to VGO;
(6) sulfidation adding wax oil hydrogenation process catalyzer comprises: constant temperature 4h ~ 16h, H at 200 DEG C ~ 240 DEG C
2the concentration of S controls to be 500 μ L/L ~ 1000 μ L/L; Constant temperature 2h ~ 16h hour, H at 260 DEG C ~ 300 DEG C
2the concentration of S controls to be 3000 μ L/L ~ 20000 μ L/L; Constant temperature 4h ~ 20h, H at 310 DEG C ~ 380 DEG C
2the concentration of S is at 5000 μ L/L ~ 20000 μ L/L, and sulfuration terminates;
(7) after sulfuration terminates, VGO carries out the cyclical operation of repeats itself hydrogen, and adjustment bed, to temperature of reaction, switches stock oil and carries out hydrotreatment reaction.
In the inventive method, the residual hydrocracking device of the steady running described in step (1) or hydroeracking unit, be generally the high-tension unit of stably manufactured running in oil refining enterprise, 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, only need by VGO go into operation sulfuration time required hydrogen sulfide the desulfurization degree of concentration controlled circulation hydrogen depriving hydrogen sulphide device.
In the inventive method, the VGO described in step (2) generally comprises wax oil hydrogenation processing reaction system.
In the inventive method, step (2) wax oil hydrogenation process catalyzer generally with refractory porous oxide for carrier, as the composite oxides or mixed oxide carrier etc. of aluminum oxide, silicon oxide, amorphous silicon aluminium, titanium oxide, molecular sieve and several element.Wax oil hydrogenation process catalyzer generally uses no acidic or weakly acidic material to be carrier, as aluminum oxide, silicon oxide, amorphous silicon aluminium etc., and load hydrogenation active metals component.The hydrogenation active component of wax oil hydrogenation process catalyzer is one or more in W, Mo, Ni and Co, is generally 3wt% ~ 50wt% with oxide basis hydrogenation active component content.Wax oil hydrogenation process catalyzer can select suitable commercial catalyst by the needs of technical process, also can prepare by existing method, also can be the regenerated catalyst of decaying catalyst after regeneration.
In the inventive method, the gas displacement described in step (3), device are airtight etc. is operating as start-up method well-known to those skilled in the art.
In the inventive method, residual hydrocracking device described in step (4) or hydroeracking unit, depriving hydrogen sulphide efficiency can be regulated by method well known to those skilled in the art, to meet the hydrogen sulfide consumption required for VGO sulfuration, general employing regulates the mode of recycle hydrogen de sulfuration hydrogen production device absorption agent (being generally amine liquid) consumption to regulate.The feed sulphur content of residual hydrocracking device or hydroeracking unit is generally 1%(quality) more than, be preferably 1.5% ~ 5%.
In the inventive method, described in step (5) by the H 2 S-containing gas of the recycle hydrogen de sulfuration hydrogen production device of residual hydrocracking device or hydrocracking process device, introduce VGO, namely machinery gas circulation is started, the recycle hydrogen de sulfuration hydrogen production device of VGO is opened, make the hydrogen sulfide content entered in the gas of residual hydrocracking device or hydroeracking unit meet the requirement of wax oil residual hydrocracking device or hydroeracking unit, be generally 500 below μ L/L.
In the inventive method, the sulfidation of described VGO can adopt wet method sulfuration or dry pre-sulfiding.As adopted wet method sulfuration, generally between 130 DEG C ~ 180 DEG C, in VGO reactive system, introduce the vulcanized oil that goes into operation, vulcanized oil absorption temperature rise ripple, by after whole beds, can carry out sulfuration according to step (6) described process; According to dry pre-sulfiding, directly carry out sulfuration according to the process described in step (6).The sulfidation of step (6) VGO is generally as follows: in 130 DEG C ~ 180 DEG C periods of VGO, stop the recycle hydrogen system of residual hydrocracking device or hydroeracking unit, adjustment recycle hydrogen de sulfuration hydrogen production device desulfurization degree, the recycle hydrogen introducing wax oil hydrogenation treatment process device of residual hydrocracking device or hydroeracking unit is gone into operation, and confirms H
2s penetrates wax oil hydrogenation treatment process reactor catalyst bed.Adjust the depriving hydrogen sulphide ability of the recycle hydrogen de sulfuration hydrogen production device of residual hydrocracking device or hydroeracking unit afterwards, reach the concentration of hydrogen sulfide needed for VGO sulfidation, with the speed of 1 DEG C/h ~ 30 DEG C/h, each bed of wax oil hydrogenation treatment process reactor is risen to 200 DEG C ~ 240 DEG C, constant temperature 4h ~ 16h hour, then with the speed of 1 DEG C/h ~ 30 DEG C/h, each for hydrocracking process reactor bed is risen to 260 DEG C ~ 300 DEG C, constant temperature 2h ~ 16h hour, with the speed of 1 DEG C/h ~ 30 DEG C/h, each bed of wax oil hydrogenation treatment process reactor is risen to 310 DEG C ~ 380 DEG C, constant temperature 4h ~ 20h hour.When VGO goes into operation in recycle hydrogen the concentration of hydrogen sulfide refer to residual hydrogenation equipment or hydroeracking unit depriving hydrogen sulphide device outlet in circulating hydrogen in H
2the concentration of S.
In the inventive method, after the VGO sulfuration described in step (7) terminates, adjust to normal workflow, by method adjustment operational condition well known to those skilled in the art, switch stock oil.
The inventive method is by the recycle hydrogen of residual hydrocracking device or hydroeracking unit, and as the vulcanization process of the vulcanisation cycle hydrogen of the sulfur-bearing agent of wax oil hydrogenation treatment process device, tool has the following advantages:
1, the vulcanization process of oxidation state wax oil hydrogenation process catalyzer provided by the invention, can ensure higher cure efficiency.
2, method provided by the invention, as long as simply transform existing installation, just can reach requirement, and reduce sulfuration investment, avoid manually injecting the murder by poisoning of vulcanizing agent to human body, the easy operation that goes into operation, has considerable economic benefit and social benefit simultaneously.
3, due in the method, adopt the output gas of the desulfurizer of residual hydrocracking device or hydroeracking unit, introduce VGO, form machinery gas circulation, and with controlling the processing power of residual hydrocracking device or hydroeracking unit recycle hydrogen de sulfuration hydrogen production device, there is provided wax oil hydrogenation treatment process device at 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, and simple operation, security is good, environmental friendliness, and has higher catalytic activity.
Accompanying drawing explanation
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, 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, i.e. machinery gas circulation, the recycle hydrogen de sulfuration hydrogen production device of VGO is opened, and controls the requirement that the hydrogen sulfide content entered in the gas of residual hydrocracking device or hydroeracking unit meets residual hydrocracking device or hydroeracking unit.When reaction bed temperature reaches 95 ~ 180 DEG C, can introduce or not introduce vulcanized oil, the H 2 S-containing gas drawing the recycle hydrogen de sulfuration hydrogen production device of residual hydrocracking device or hydroeracking unit enters reactor, and vulcanized oil volume space velocity is 0.5 ~ 5h
-1, hydrogen to oil volume ratio is 100 ~ 1500.
Concrete grammar of the present invention and effect is further illustrated 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, through residual hydrocracking device 1(for residual hydrocracking device), 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 introduces VGO 4, carry out sulfuration, again through VGO reaction product gas-liquid separator 5, enter VGO recycle hydrogen de sulfuration hydrogen production device 6, carry out depriving hydrogen sulphide process, turn back to residual hydrocracking device 1.
Below by specific embodiment, the inventive method is explained in detail.
The oxidation state hydrotreating catalyst adopted in embodiment in the present invention is the FF-14 of Fushun Petrochemical Research Institute's development and production.FF-14 catalyzer is carrier with aluminum oxide, take Mo-Ni-Co as active ingredient.In each embodiment, FF-14 usage quantity is 100 grams.The per-cent wherein not indicating benchmark is weight percentage.
Stock oil character simultaneously used in the embodiment of the present invention is in table 1, and in embodiment, used catalyst technology assessment condition is in table 2.
Table 1 stock oil
| Stock oil | Iran VGO |
| Density (20 DEG C), g.cm -3 | 0.9168 |
| Boiling range (IBP/EBP), DEG C | 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 |
| Hydrogen dividing potential drop, MPa | 14.0 |
| Hydrogen to oil volume ratio | 600 |
| Volume space velocity, h -1 | 1.20 |
| Temperature of reaction, DEG C | 360 |
Comparative example 1
FF-14 catalyzer loads in hydrotreating reactor, then carries out airtight.Airtight qualified after, hydrogen dividing potential drop is adjusted to 14.0MPa, and temperature is adjusted to 170 DEG C, starts to introduce vulcanized oil, bed temperature steadily after, start sulfuration and inject (vulcanizing agent is DMDS) after vulcanizing agent, hydrogen to oil volume ratio is 600.Start to be warming up to 230 DEG C with 5 DEG C/h, and to penetrate after each beds constant temperature 6 hours until vulcanizing agent.After terminating constant temperature, hydrogen sulfide and circulating hydrogen gas mixture continue to be warming up to 290 DEG C with 5 DEG C/h, constant temperature 6 hours.Constant temperature terminates, and continues to be warming up to 320 DEG C with 4 DEG C/h, constant temperature 6 hours.Constant temperature terminates, and switches stock oil by operation.Rise to 360 DEG C of runnings 48 hours after switching raw material, carry out adopting 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, through residual hydrocracking device recycle hydrogen de sulfuration hydrogen production device 3, turns back to residual hydrocracking device 1.Meanwhile, FF-14 catalyzer loads in hydrotreating reactor, through super-dry, then carries out airtight.Airtight qualified after, hydrogen dividing potential drop is adjusted to 14.0 MPa, and temperature is adjusted to 160 DEG C, starts to introduce vulcanized oil.After bed temperature is steady, adjustment residual hydrocracking device recycle hydrogen de sulfuration hydrogen production device 3, hydrogen sulfide containing circulating hydrogen introduces VGO 4, carry out sulfuration, again through VGO reaction product gas-liquid separator 5, enter VGO recycle hydrogen de sulfuration hydrogen production device 6, carry out depriving hydrogen sulphide 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 the depriving hydrogen sulphide ability of the recycle hydrogen de sulfuration hydrogen production device of residual hydrocracking device afterwards, reach the concentration of hydrogen sulfide needed for VGO sulfidation, with the speed of 5 DEG C/h, each for wax oil hydrogenation treatment reactor bed is risen to 230 DEG C, H
2the concentration of S controls to be 5000 μ L/L, constant temperature 10 hours; Then with the speed of 3 DEG C/h, each for wax oil hydrogenation treatment reactor bed is risen to 290 DEG C, H
2the concentration of S controls to be 10000 μ L/L, constant temperature 10 hours; With the speed of 5 DEG C/h, each bed of wax oil hydrogenation treatment process reactor is risen to 320 DEG C, H
2the concentration of S controls to be 15000 μ L/L, constant temperature 10 hours.Adjustment temperature of reactor, introduces stock oil.After introducing raw material, temperature of reaction is adjusted to 360 DEG C of runnings 48 hours, and carry out adopting 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, through residual hydrocracking device recycle hydrogen de sulfuration hydrogen production device 3, turns back to residual hydrocracking device 1.Meanwhile, FF-14 catalyzer loads in hydrotreating reactor, through super-dry, then carries out airtight.Airtight qualified after, hydrogen dividing potential drop is adjusted to 14.0MPa, and temperature is adjusted to 180 DEG C.Now, adjustment residual hydrocracking device recycle hydrogen de sulfuration hydrogen production device 3, hydrogen sulfide containing circulating hydrogen introduces VGO 4, carry out sulfuration, again through VGO reaction product gas-liquid separator 5, enter VGO recycle hydrogen de sulfuration hydrogen production device 6, carry out depriving hydrogen sulphide 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 the depriving hydrogen sulphide ability of the recycle hydrogen de sulfuration hydrogen production device of residual hydrocracking device afterwards, reach the concentration of hydrogen sulfide needed for VGO sulfidation, with the speed of 3 DEG C/h, each bed of wax oil hydrogenation treatment process reactor is risen to 220 DEG C, H
2the concentration of S controls to be 5000 μ L/L, constant temperature 12 hours; Then with the speed of 3 DEG C/h, each bed of wax oil hydrogenation treatment process reactor is risen to 290 DEG C, H
2the concentration of S controls to be 10000 μ L/L, constant temperature 12 hours; With the speed of 3 DEG C/h, each bed of wax oil hydrogenation treatment process reactor is risen to 380 DEG C, H
2the concentration of S controls to be 16000 μ L/L, constant temperature 8 hours.After sulfuration terminates, adjustment temperature, introduces stock oil.After introducing raw material, temperature of reaction is adjusted to 360 DEG C of runnings 48 hours, and carry out adopting 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, through residual hydrocracking device recycle hydrogen de sulfuration hydrogen production device 3, turns back to residual hydrocracking device 1.Meanwhile, FF-14 loads in reactor, through super-dry, then carries out airtight.Airtight qualified after, hydrogen dividing potential drop is adjusted to 14.0MPa, and temperature is adjusted to 160 DEG C, starts to introduce vulcanized oil.After bed temperature is steady, adjustment residual hydrocracking device recycle hydrogen de sulfuration hydrogen production device 3, hydrogen sulfide containing circulating hydrogen introduces VGO 4, carry out sulfuration, again through VGO reaction product gas-liquid separator 5, enter VGO recycle hydrogen de sulfuration hydrogen production device 6, carry out depriving hydrogen sulphide 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 the depriving hydrogen sulphide ability of the recycle hydrogen de sulfuration hydrogen production device of residual hydrocracking device afterwards, reach the concentration of hydrogen sulfide needed for VGO sulfidation, with the speed of 8 DEG C/h, each bed of wax oil hydrogenation treatment process reactor is risen to 220 DEG C, H
2the concentration of S controls to be 5000 μ L/L, constant temperature 8 hours; Then with the speed of 5 DEG C/h, each bed of wax oil hydrogenation treatment process reactor is risen to 290 DEG C, H
2the concentration of S controls to be 10000 μ L/L, constant temperature 10 hours; With the speed of 10 DEG C/h, each bed of wax oil hydrogenation treatment process reactor is risen to 320 DEG C, H
2the concentration of S controls to be 15000 μ L/L, constant temperature 10 hours.Adjustment temperature, introduces stock oil.After introducing raw material, temperature of reaction is adjusted to 360 DEG C of runnings 48 hours, and carry out adopting 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, through residual hydrocracking device recycle hydrogen de sulfuration hydrogen production device 3, turns back to residual hydrocracking device 1.Meanwhile, FF-14 catalyzer loads in hydrotreating reactor, through super-dry, then carries out airtight.Airtight qualified after, hydrogen dividing potential drop is adjusted to 14.0MPa, and temperature is adjusted to 170 DEG C.Now, adjustment residual hydrocracking device recycle hydrogen de sulfuration hydrogen production device 3, hydrogen sulfide containing circulating hydrogen introduces VGO 4, carry out sulfuration, again through VGO reaction product gas-liquid separator 5, enter VGO recycle hydrogen de sulfuration hydrogen production device 6, carry out depriving hydrogen sulphide 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 the depriving hydrogen sulphide ability of the recycle hydrogen de sulfuration hydrogen production device of residual hydrocracking device afterwards, reach the concentration of hydrogen sulfide needed for VGO sulfidation, with the speed of 3 DEG C/h, each bed of wax oil hydrogenation treatment process reactor is risen to 230 DEG C, H
2the concentration of S controls to be 5000 μ L/L, constant temperature 10 hours; Then with the speed of 5 DEG C/h, each bed of wax oil hydrogenation treatment process reactor is risen to 290 DEG C, H
2the concentration of S controls to be 10000 μ L/L, constant temperature 10 hours; With the speed of 3 DEG C/h, each bed of wax oil hydrogenation treatment process reactor is risen to 380 DEG C, H
2the concentration of S controls to be 16000 μ L/L, constant temperature 8 hours.After sulfuration terminates, adjustment temperature, introduces stock oil.After introducing raw material, temperature of reaction is adjusted to 360 DEG C of runnings 48 hours, and carry out adopting 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, through residual hydrocracking device recycle hydrogen de sulfuration hydrogen production device 3, turns back to residual hydrocracking device 1.Meanwhile, FF-14 catalyzer loads in hydrotreating reactor, through super-dry, then carries out airtight.Airtight qualified after, hydrogen dividing potential drop is adjusted to 14.0MPa, and temperature is adjusted to 150 DEG C, starts to introduce vulcanized oil.After bed temperature is steady, adjustment residual hydrocracking device recycle hydrogen de sulfuration hydrogen production device 3, hydrogen sulfide containing circulating hydrogen introduces VGO 4, carry out sulfuration, again through VGO reaction product gas-liquid separator 5, enter VGO recycle hydrogen de sulfuration hydrogen production device 6, carry out depriving hydrogen sulphide 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 the depriving hydrogen sulphide ability of the recycle hydrogen de sulfuration hydrogen production device of residual hydrocracking device afterwards, reach the concentration of hydrogen sulfide needed for VGO sulfidation, with the speed of 10 DEG C/h, each bed of wax oil hydrogenation treatment process reactor is risen to 230 DEG C, H
2the concentration of S controls to be 5000 μ L/L, constant temperature 8h hour; Then with the speed of 5 DEG C/h, each bed of wax oil hydrogenation treatment process reactor is risen to 290 DEG C, H
2the concentration of S controls to be 10000 μ L/L, constant temperature 4 hours; With the speed of 10 DEG C/h, each bed of wax oil hydrogenation treatment process reactor is risen to 320 DEG C, H
2the concentration of S controls to be 15000 μ L/L, constant temperature 10 hours.Adjustment temperature, introduces stock oil.After introducing raw material, temperature of reaction is adjusted to 360 DEG C of runnings 48 hours, and carry out adopting 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: 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, through hydroeracking unit recycle hydrogen de sulfuration hydrogen production device 3, turns back to hydroeracking unit 1.Meanwhile, FF-14 catalyzer loads in hydrotreating reactor, through super-dry, then carries out airtight.Airtight qualified after, hydrogen dividing potential drop is adjusted to 14.0MPa, and temperature is adjusted to 160 DEG C.Now, adjustment hydroeracking unit recycle hydrogen de sulfuration hydrogen production device 3, hydrogen sulfide containing circulating hydrogen introduces VGO 4, carry out sulfuration, again through VGO reaction product gas-liquid separator 5, enter VGO recycle hydrogen de sulfuration hydrogen production device 6, carry out depriving hydrogen sulphide 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 the depriving hydrogen sulphide ability of the recycle hydrogen de sulfuration hydrogen production device of hydroeracking unit afterwards, reach the concentration of hydrogen sulfide needed for VGO sulfidation, with the speed of 3 DEG C/h, each bed of wax oil hydrogenation treatment process reactor is risen to 210 DEG C, H
2the concentration of S controls to be 6000 μ L/L, constant temperature 10 hours; Then with the speed of 5 DEG C/h, each bed of wax oil hydrogenation treatment process reactor is risen to 300 DEG C, H
2the concentration of S controls to be 10000 μ L/L, constant temperature 12 hours; With the speed of 3 DEG C/h, each bed of wax oil hydrogenation treatment process reactor is risen to 370 DEG C, H
2the concentration of S controls to be 16000 μ L/L, constant temperature 8 hours.After sulfuration terminates, adjustment temperature, introduces stock oil.After introducing raw material, temperature of reaction is adjusted to 360 DEG C of runnings 48 hours, and carry out adopting finished product crude oil sample analysis, catalyst activity the results are shown in Table 3.
Table 3 wax oil hydrogenation process catalyst activity compares
| Embodiment is numbered | Treated oil sulphur content, μ g/g | 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 |
As can be seen from the result of table 3, adopt sulfuration start-up method provided by the invention, its catalyst activity is also better than conventional wax oil hydrogenation process catalyst vulcanization start-up method.But because the inventive method only needs to transform existing installation, just requirement can be reached, the purchase of the investment and vulcanizing agent that simultaneously reduce vulcanizing plant uses, avoid manually injecting the murder by poisoning of vulcanizing agent to human body, the easy operation that goes into operation, and use oil refining by product to greatest extent, have considerable economic benefit and social benefit.
Claims (12)
1. a catalyst vulcanization method for wax oil hydrogenation treatment process, comprises the following steps:
(1) residual hydrocracking device or hydrocracking process unit normal run;
(2) wax oil hydrogenation treatment process device comprises wax oil hydrogenation treatment reactor, reactor charge oxidation state wax oil hydrogenation process catalyzer;
(3) wax oil hydrogenation treatment process device carries out gas displacement, catalyzer drying, device airtight work;
(4) desulfurization degree of recycle hydrogen de sulfuration hydrogen production device in the residual hydrocracking device of steady running or hydroeracking unit is adjusted;
(5) by the H 2 S-containing gas that the recycle hydrogen de sulfuration hydrogen production device of residual hydrocracking device or hydroeracking unit is discharged, introduce VGO, vulcanisation operation is carried out to VGO;
(6) sulfidation adding wax oil hydrogenation process catalyzer comprises: constant temperature 4h ~ 16h at 200 DEG C ~ 240 DEG C, and the concentration of hydrogen sulfide controls to be 500 μ L/L ~ 1000 μ L/L; Constant temperature 2h ~ 16h at 260 DEG C ~ 300 DEG C, the concentration of hydrogen sulfide controls to be 3000 μ L/L ~ 20000 μ L/L; Constant temperature 4h ~ 20h at 310 DEG C ~ 380 DEG C, the concentration of hydrogen sulfide is 5000 μ L/L ~ 20000 μ L/L, and sulfuration terminates;
(7) after sulfuration terminates, VGO carries out the cyclical operation of repeats itself hydrogen, and adjustment bed, to temperature of reaction, switches stock oil and carries out 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 step (1) or hydrocracking process device, be the high-tension unit of stably manufactured running in oil refining enterprise, pressure rating is identical with VGO, and pressure is 10 ~ 25MPa.
3. in accordance with the method for claim 1, it is characterized in that: the VGO described in 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%.
5. in accordance with the method for claim 1, it is characterized in that, the sulfidation of step (6) described VGO adopts wet method sulfuration, between 130 DEG C ~ 180 DEG C, the vulcanized oil that goes into operation is introduced in VGO reactive system, vulcanized oil by after whole beds, then carries out follow-up warming temperature.
6. in accordance with the method for claim 1, it is characterized in that, the sulfidation of the VGO described in step (6) adopts dry pre-sulfiding.
7. in accordance with the method for claim 1, it is characterized in that, step (2) described wax oil hydrogenation process catalyzer with no acidic or weakly acidic refractory porous oxide for carrier, hydrogenation active component is one or more in W, Mo, Ni and Co, is generally 3wt% ~ 50wt% with oxide basis hydrogenation active component content.
8. in accordance with the method for claim 1, it is characterized in that, the residual hydrocracking device described in step (4) or hydroeracking unit, adopt and regulate the mode of 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: described in step (5) by the H 2 S-containing gas of the recycle hydrogen de sulfuration hydrogen production device of residual hydrocracking device or hydrocracking process device, introduce VGO, namely machinery gas circulation is started, the recycle hydrogen de sulfuration hydrogen production device of VGO is opened, and makes the hydrogen sulfide content entered in the gas of residual hydrocracking device or hydroeracking unit meet 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, in 130 DEG C ~ 180 DEG C periods of VGO, stop the recycle hydrogen system of residual hydrocracking device or hydroeracking unit, adjustment recycle hydrogen de sulfuration hydrogen production device desulfurization degree, goes into operation the recycle hydrogen introducing wax oil hydrogenation treatment process device of residual hydrocracking device or hydroeracking unit, and confirms H
2s penetrates wax oil hydrogenation treatment process reactor catalyst bed, adjusts the depriving hydrogen sulphide ability of the recycle hydrogen de sulfuration hydrogen production device of residual hydrocracking device or hydroeracking unit afterwards, reaches the concentration of hydrogen sulfide needed for VGO sulfidation.
11. in accordance with the method for claim 1, it is characterized in that, and the heat-up rate in the sulfidation of step (6) hydrotreater is 1 DEG C/h ~ 30 DEG C/h.
12. 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 2% ~ 5%.
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