CN106947522B - A kind of start-up method of the hydrocracking unit containing two class site catalysts - Google Patents
A kind of start-up method of the hydrocracking unit containing two class site catalysts Download PDFInfo
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- CN106947522B CN106947522B CN201610002929.7A CN201610002929A CN106947522B CN 106947522 B CN106947522 B CN 106947522B CN 201610002929 A CN201610002929 A CN 201610002929A CN 106947522 B CN106947522 B CN 106947522B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of start-up vulcanization methods of hydrocracking unit.The catalyst of ex situ presulfiding type is used by grading; the hydrogen sulfide gas generated in temperature-rise period using it protects the hydrogenation catalyst containing two class activated centres in advance; simultaneously according to the difference of two class site catalyst preparation methods; can selectivity the certain auxiliary gas of injection, be converted into dry method to which wet method go into operation and go into operation.The method of the present invention can improve the activity of catalyst, be suitable for the vulcanization start-up process of various two classes activated centre hydrogenation catalyst.
Description
Technical field
The present invention relates to a kind of start-up vulcanization methods of hydrogenation catalyst, are catalyzed especially for containing two class activated centres
The start-up method of the hydrocracking unit of agent.
Background technology
Currently, since the degree of heaviness of crude oil in world wide is increasingly sharpened, while the strict demand of environmental regulation, promote
The quality for the raw material for adding the device of hydrogen species type to be processed is set to be deteriorated year by year, all kinds of impurity contained in raw material, including metal,
The content of the reactants such as sulphur, nitrogen is at ascendant trend, and under the overall situation of this harshness, the catalyst preparation developer of various countries is
The update of catalyst activity and progress are considered as the significant challenge itself faced.
For hydrofinishing（Processing）For catalyst, it is obvious to all to add the contribution that hydrogen people makes, by continuous
Make great efforts and attempt, it is proposed that many new catalyst make theory and method, and it is most most advanced extensively to be currently applied to commercial plant
Hydrofinishing（Processing）Catalyst is typically the product containing two class activated centres, and this catalyst can be in identical reaction
At a temperature of, reach deeper impurity removal depth, to which under the premise of not changing catalysis material, raising by a relatively large margin is catalyzed
The Hydrogenation of agent.
Although the benefit of such catalyst is also encountered certain it will be apparent that still in industrial actual application
Difficulty because it during preparation, adds special auxiliary agent, the purpose is to cocatalyst vulcanization when can give birth to
At more two classes activated centre, to improve Hydrogenation, but this analog assistant can generally have labile feature of being heated,
After reaching certain temperature, this auxiliary agent, which is easy for decomposing in advance, causes declining to a great extent for catalyst activity, to lose
It uses advantage.
The vulcanization of conventional hydrogenation catalyst, liquid separation phase（Wet method）Vulcanization and gas phase（Dry method）Two kinds of vulcanization.For using
For the diesel refining class device of such catalyst, since the start-up process of itself is that liquid phase goes into operation, it can be decomposed in auxiliary agent
Before, using going into operation, catalyst irrigation is avoided the decomposition in temperature-rise period by oil to be protected；But for making
With the hydrocracking unit of such catalyst（The hydrocracking unit dabbled in this method may include hydro-upgrading unit）
For, in order to avoid the decomposition of auxiliary agent, it is necessary to conventional gas-phase presulfiding process are changed to liquid phase sulfidation, vulcanization is moved back
Step can bring the following to go into operation drawback：
1, the various compounds etc. to go into operation in oil product, can cause catalyst coking；
2, vulcanization terminal shifts to an earlier date, and reinforcing degree weakens in catalyst device, and incipient cure degree is insufficient；
3, gas-liquid-solid three-phase exists simultaneously, and influences flow distribution, causes catalyst vulcanization degree uneven；
4, vulcanization passivating process is carried out at the same time, and reagent consumption increases；
5, high activity cracking agent and liquid phase oil product exist simultaneously, and overtemperature risk becomes larger.
In conclusion the pattern that goes into operation for adjusting, changing to adapt to catalyst type change, can cause material consumption to increase
Add, operational risk becomes larger, and catalyst activity reduces, and compared with the catalyst activity that auxiliary agent is improved is added, which is more important, still
It is difficult to compare.
Chinese patent CN103773436A and CN102311766A describe going into operation for two class activated centre hydrogenation catalysts
Method, although more two classes activated centre can be generated under such an approach, start-up process is required to introduce liquid component,
The pattern that wet method goes into operation is still fallen within, can not thoroughly solve the intrinsic drawback of liquid phase sulfidation and to catalyst activity
Damage.
Chinese patent CN101492613A and CN101492607A describe the start-up method of hydrocracking process, although opening
Work process need not additionally inject vulcanizing agent, but there is still a need for load in oxidized catalyst during ex situ presulfiding
Certain sulfide vulcanizes hydrogen atmosphere to meet needed for start-up process.
Chinese patent CN101003749A describes a kind of overall process and is hydrocracked start-up method without using vulcanizing agent,
Although easy to operate, process is easy, it can be difficult to ensureing the lytic activity and activity of oxidation state and elemental metals catalyst
Stability.
Invention content
For problems of the prior art, the present invention provides a kind of contain two class activated centre hydrogenation catalysts plus hydrogen
Cracking unit gas phase start-up method.This method is anti-by weighted BMO spaces using industrial widely applied ex situ presulfiding technology
It answers whole protective agents in device to do outside device and carries sulphuring treatment, using the hydrogen sulfide gas generated in temperature-rise period to its underpart（Downstream）
Two class site catalysts of filling are protected in advance, while the auxiliary agent that while being prepared according to two class site catalysts is added
Difference can assist gas with Selective implantation, avoid auxiliary agent from decomposing, loss of activity and material consumption are increased in start-up process
Problem not only saves energy, and it is active significantly to improve using for catalyst.
The start-up method of hydrocracking unit provided by the invention containing two class site catalysts, including it is following interior
Hold：
a）Hydrocracking unit includes hydrofining reactor and hydrocracking reactor；According to the direction of logistics, add hydrogen
Finishing reactor loads hydrogenation protecting agent and hydrotreating catalyst successively from top to bottom；Hydrocracking reactor from top to bottom according to
Secondary filling hydrocracking catalyst and plus hydrogen post-processing catalyst；Wherein hydrogenation protecting agent is ex situ presulfiding catalyst, adds hydrogen
Processing catalyst is two class site catalysts；
b）By hydrocracking unit operating mode according to the conventional pattern setting that goes into operation, and step up hydrofining reactor entrance
Temperature is adjusted to 180~200 DEG C by cold hydrogen, and the entrance for containing two class site catalyst beds in finishing reactor is controlled
Temperature is not higher than 160 DEG C；
c）Constant temperature, after reactor outlet concentration of hydrogen sulfide qualification, adjustment hydrofining reactor inlet temperature is 170 DEG C
~190 DEG C, and stop the injection of cold hydrogen；
d）As step c）After the completion, vulcanizing agent is injected to reaction system, then according to conventional gas-phase presulfiding method to urging
Agent goes into operation.
Wherein, the type of auxiliary agent is added when being prepared according to two class activated centre hydrogenation catalysts, can also state on the implementation
Step b）Auxiliary protection gas is optionally injected into when process.
According to the method for the present invention, wherein step a）In the hydrocracking unit, with the stereometer of catalyst, filled
Hydrogenation protecting catalyst, Hydrobon catalyst, hydrocracking catalyst and the body for being hydrocracked post-processing catalyst filled out
Fraction is generally respectively 4%~10%, 30%~60%, 35%~55% and 4%~10%.
Step a）The ex situ presulfiding catalyst refers to that hydrogenation protecting catalyst, will using infusion process before manufacture
Vulcanizing agent is carried on the protective agent of oxidation state, then the catalyst obtained through low temperature drying processing procedure.Ex situ presulfiding is urged
The common preparation process of agent is urged according to preparing oxidation state the step of carrier preparation-metal impregnation-high-temperature roasting successively first
Agent, this has been technically quite reliable and well known；Then the addition for carrying out specific vulcanizing agent, will using infusion process
Selected vulcanizing agent loads on the catalyst of oxidation state, then after carrying out low temperature drying processing procedure.Described is specific
Vulcanizing agent can be the one or several kinds in elemental sulfur, sulfur-containing compound, and sulfur-containing compound is selected from mercaptan, ammonium polysulfide etc..
In view of the requirement to discharging hydrogen sulfide, preferably solid-state sulphur powder.On the basis of the weight of catalyst, content of the sulphur in terms of elementary sulfur
For 5wt~25wt%.The routine operation for being prepared as this field of ex situ presulfiding catalyst.
Step a）The ex situ presulfiding guard catalyst, it is most of essentially identical with original protective agent in physical property,
But two attributes of more sulfur contents and weightening.In general, sulfur content is 5%~25 wt% of catalyst weight, total catalysis
Agent is increased weight（Containing including sulphur and other assistant soakage liquid summations）For 15%~35wt% of catalyst weight.In start-up process,
Contained sulfide can generally be converted into three parts in catalyst：A part is bound directly with catalyst activity metal component
Form metal sulfide；Another part sulfide can be converted into hydrogen sulfide, then react to form metal with active metal component again
Sulfide；Some sulfide decomposes the hydrogen sulfide generated and is taken away and flowed to the downstream by logistics such as hydrogen.The choosing of sulfide
It selects and the difference of preparation condition, determines that the degree in the sulfide conversion direction loaded on catalyst is different.
Step a）The hydrocracking unit contains hydrogenation protecting agent, hydrotreating catalyst（Or hydrofinishing catalysis
Agent）And hydrocracking catalyst, usually a small amount of post-processing that is hydrocracked also is filled in the downstream of hydrocracking catalyst urge
Agent.
The hydrogenation protecting agent can contain active component, can not also contain active component.Hydrogenation protecting agent is general
Using using VI B races and/or group VIII metal as active component, using aluminium oxide or silicon-containing alumina as carrier.Group VIB metal is general
For Mo and/or W, group VIII metal is generally Co and/or Ni.On the basis of the weight of catalyst, group VIB tenor is with oxygen
Compound is calculated as 0wt%~10wt%, and group VIII metal content is calculated as the wt% of 0wt%~8 with oxide.Its property is as follows：Specific surface is
1~300m20.1~0.9mL/g of/g, Kong Rongwei, appearance can be that porous ball, Raschig ring, bunge bedstraw herb, Bird's Nest, abnormal shape etc. are a variety of
Shape.Alternative commercial catalysts type is various, such as Fushun Petrochemical Research Institute（FRIPP）The FZC- of development
100, the hydrogenation protectings agent such as FZC-102B, FZC-105, FZC-204；Tool prepared by the common sense of this field can also be pressed as needed
There are all kinds of hydrogenation protecting agent of protection major catalyst function.
Described refers to the Hydrobon catalyst containing two class activated centres containing two class activated centre hydrogenation catalysts
Or hydrotreating catalyst.The Hydrobon catalyst includes common diesel Hydrobon catalyst, generally with VI B races
And/or group VIII metal be active component, using aluminium oxide or silicon-containing alumina as carrier, group VIB metal be generally Mo and/or
W, group VIII metal are generally Co and/or Ni.On the basis of the weight of catalyst, group VIB tenor is calculated as with oxide
8wt%~28wt%, group VIII metal content are calculated as the wt% of 2wt%~15 with oxide, and property is as follows：Specific surface be 100~
650m20.15~0.8mL/g of/g, Kong Rongwei.The hydrotreating catalyst includes carrier and the hydrogenation metal that is loaded.With
On the basis of the weight of catalyst, metal component of group VIB in the periodic table of elements is generally included, if tungsten and/or molybdenum are in terms of oxide
It is 10%~35%, preferably 15%~30%；Group VIII metal such as nickel and/or cobalt are calculated as 1%~7%, preferably 1.5% with oxide
~6%.Carrier is inorganic refractory oxide, is selected generally from aluminium oxide, amorphous silicon aluminium, silica, titanium oxide etc..Either
Above-mentioned Hydrobon catalyst or hydrotreating catalyst should all have an identical feature, i.e., add in preparation process
Certain auxiliary agent is entered, this auxiliary agent can be the inorganic complexing salts substances by selecting, and catalyst is made in use may be used
To form more two classes activated centre, improves it and use activity, step b）Auxiliary agent decomposition temperature, that is, the additive
By heat decomposition temperature, this general temperature is at 160 DEG C hereinafter, it is preferred that at 140 DEG C or less.Alternative commercial catalysts type
It is various, such as Fushun Petrochemical Research Institute（FRIPP）The UDS-2 Hydrobon catalysts of development, FF-46, FF-56 etc.
Hydrotreating catalyst；The common sense that this field can also be pressed as needed prepares the oxidized catalyst containing two class activated centres
Hydrotreating（Or hydrofinishing）Catalyst.
Either above-mentioned Hydrobon catalyst or hydrotreating catalyst is provided with an identical feature, that is, exists
Certain organic additive is added in preparation process.The organic additive can be citric acid, hydramine substance etc., commonly
Hydramine substance has the homologues such as methylethanolamine, ehtylethanolamine, dimethylethanolamine.The organic additive is generally in catalyst
Dipping process when preparation is added, and organic additive usage amount is 1~10 wt% of catalyst total metal contents in soil.Pass through dipping
Cancel subsequent catalyst high-temperature drying procedures after auxiliary agent is added, instead carries out low temperature dewatering processing.By low temperature
After dehydration, the organic additive and active metal of addition（Especially main metal）Between complexing occurs, be greatly lowered
Interaction between main metal and promoter metal and carrier, makes it be more easy to cure.Thus, this kind of catalyst is after over cure
More two classes activated centre can be formed, hydrogenation activity in use is improved, and products obtained therefrom quality is more
It is good.The preparation method of this two classes site catalyst is through being known content in the art, such as Japan Patent Shen
Please 06-339635, European patent application 0601722, Chinese patent CN101491766B etc. have been described.The method of the present invention
In, when unvulcanized, sulphur and/or sulfur-containing compound are not contained in the two class site catalysts.
The hydrocracking catalyst includes Cracking Component and hydrogenation component.Cracking Component generally includes amorphous silica-alumina
And/or molecular sieve, such as Y types or USY molecular sieve.Adhesive is usually aluminium oxide or silica.Hydrogenation component is selected from VI race, VII race
Or VIII race metal, metal oxide or metal sulfide, more preferably iron, chromium, molybdenum, tungsten, cobalt, nickel or its sulfide or oxygen
One or more of compound.On the basis of the weight of catalyst, the content of hydrogenation component is 5~40 wt%, preferably 10~30
Wt%, molecular sieve content are 0~70 wt%, preferably 20~70 wt%.Conventional hydrocracking catalyst can select existing various
The catalyst such as commercial catalysts, such as FC-12, FC-16, FC-24, FC-26, FC-32, FC-46 of FRIPP developments.?
The common sense that this field can be pressed as needed prepares specific hydrocracking catalyst.
Step b）The routine goes into operation pattern for the reactor operating mode before existing hydrocracking unit note sulphur, is followed by system
Several big parameters such as ring hydrogen amount, reactor inlet pressure, reactor inlet temperature collectively constitute.Each parameter is generally：System circulation
Hydrogen amount recycles for 50~100% full doses, preferably 80~100% full doses cycle；Reactor inlet pressure is 90~100% design pressures,
Preferred design pressure；Reactor inlet temperature is ≯ 160 DEG C（It is less than or equal to 160 DEG C）, heating rate is ≯ 20 DEG C/h.But
It may be selected to properly increase reactor inlet temperature under normal mode, promoted according to being subject to the cold hydrogen cooling extent of lower part bed, one
As be ≯ 190 DEG C, and squeeze into cold hydrogen in two bed inlets and reduce temperature, it is the original parsed based on cryogenic absorption high temperature to do so
Reason can be conducive to the fast quick-release of hydrogen sulfide in hydrogenation protecting agent under the premise of ensureing that two class activated centres are not decomposed
It puts, is greatly saved the time for the waiting that goes into operation.
Step c）The reactor outlet can be treatment reactor outlet, can also be cracker outlet；When
When the post-processing catalyst loaded in hydrocracking reactor is two class site catalyst, hydrogenation protecting agent is being made entirely
It is standby grow up to be a useful person outer presulfurization while, the part inorganic agent of its underpart should be also prepared into ex situ presulfiding type depending on concrete condition,
At this point, thief hatch should be cracker outlet；When the post-processing catalyst loaded in hydrocracking reactor is lived for non-two class
When property center catalyst, it is only necessary to hydrogenation protecting agent are all prepared into ex situ presulfiding type, at this point, thief hatch should be processing
Reactor outlet, in the present invention, it is preferred to the method；Even if the post-processing catalyst selected is two class site catalysts,
It, will not even if auxiliary agent is decomposed for some hydrocracking units not high to post-processing catalyst Active pharmaceutical
It has any impact, so still it is contemplated that thief hatch is set in treatment reactor outlet；Concentration of hydrogen sulfide qualification refers to can
To determine concentration of hydrogen sulfide, but preferably concentration of hydrogen sulfide is 100 μ L/L or more, you can thinks urging containing two class activity phases
Agent has been protected.
Step c）Depending on the constant temperature time answers the loadings of the outer presulfurization catalyst of visual organ, generally 4~8 is small
When.
Step d）The vulcanizing agent is vulcanizing agent commonly used in the art, can be SZ-54, DMDS or CS2。
Step d）The operating condition of the gas-phase presulfiding method is：5.0~16.0 MPa of reaction pressure, gas flow are controllable
50~100% load of compressor is recycled, and general view apparatus treating capacity is different, this numerical value is in 5~400,000 Nm3It is between/h
It is possible.Curing temperature section is 100 DEG C~380 DEG C.Preferred operating condition is 7.0~15.5 MPa of reaction pressure, excellent
System circulation hydrogen amount is selected to be recycled for 80%~100% full dose, curing temperature section is 170 DEG C~370 DEG C.Whole process is according to one's own profession
Conventional dry start-up method known to various devices is gone into operation in the industry.
The auxiliary agent being added in two class site catalysts refers to preparation process a）Described in hydrofinishing/hydrotreating
What is be added when catalyst can form the substance in two class activated centres.The auxiliary protection gas can be hydrogen sulfide or
The non-neutrals gas such as anhydrous liquid ammonia.Auxiliary agent can be divided into alkalescent or faintly acid two major classes, work as auxiliary agent because of the difference of catalyst type
When using alkalescent substance, can supplement appropriate inject hydrogen sulfide as auxiliary protection gas, be more conducive to be adsorbed on activity
To play the role of protection on center.In addition, the hydrogen sulfide gas of supplement injection also has the vulcanization of catalyst in system
Certain benefit.When auxiliary agent uses acidulous material, can supplement appropriate inject anhydrous liquid ammonia as auxiliary protection gas,
It is more conducive to be adsorbed on activated centre to play the role of protection.In addition, the anhydrous liquid ammonia gas of supplement injection is for body
The passivation of Cracking catalyst in system also has certain effect.
Compared with prior art, start-up method of the invention has the characteristics that：
1, catalyst grade is combined with technology with ex situ presulfiding technology by the present invention, and the sulphur generated is decomposed using sulphur agent is carried
Change hydrogen and low-temperature protection is carried out to the hydrotreating containing two class activated centres/Hydrobon catalyst as protective gas, in enterprise
Under the premise of without any changes to device, only pass through the optimization of the conditions such as temperature in technique and the optimum organization of catalyst type
The pattern that will go into operation is changed, and the sulfidation that goes into operation of this hydrocracking unit has not only been completed, but also can improve making for catalyst
With activity, a more convenient and economic approach is had found for the enhancing efficiency by relying on tapping internal latent power of refinery facilities.
2, the characteristics of the method for the present invention makes full use of hydrogen sulfide adsorption to protect converts gas phase and goes into operation the liquid phase pattern that goes into operation to
Pattern, the case where avoiding start-up process catalyst coking so that sulfidation is more abundant, hydrogen sulfide distributed effect more preferably,
The reduction of radial temperature difference is made that contribution when being produced for device in future；Improve the time for strengthening vulcanization in catalyst device, enhancing
Hydrogenation activity during use；Meanwhile the cancellation of liquid phase stream, the occurrence of avoiding catalyst bed overtemperature.
3, while being protected using hydrogen sulfide, according to the principle that the difference of assistant types, is carried out auxiliary using soda acid absorption
Protection is helped, the safety of further increased protection can fully play out the due activity of catalyst.
4, the method for the present invention is while resource rational utilization, reduces making for vulcanizing agent in sulfidation and passivator
Dosage can reduce the consumption of vulcanizing agent and passivator, no to greatest extent on the basis of promotion catalyst vulcanization is active
A large amount of human and material resources can be only saved, while a large amount of discharges for also avoiding sour water and the pollution to environment, reduced
Operation difficulty can also reduce the whole investment in start-up process in the long run.
5, the method for the present invention and conventional reaction system are all using pre- sulphur outside ex situ presulfiding catalyst or existing device
Change grading patented technology to compare, since main purpose is not to vulcanize catalyst but protect, so improving
While catalyst is using activity, the quantity of presulfurization processing can be reduced to a certain extent and carries sulfur content, further, since protective agent
In contained tenor it is relatively low, can reduce to greatest extent and carry sulphur agent decomposition and catalyst vulcanization heat in start-up process
Superposition avoids the generation that catalyst in start-up process concentrates exothermic phenomenon, the processing safety of sulfidation is improved, to add
Hydrogen cracking unit quiet run is made that contribution.
6, the method for the present invention and popular response system are all using ex situ presulfiding catalyst or existing ex situ presulfiding
Grading patented technology is compared, since main purpose is not to be vulcanized to catalyst but protected, so it is being improved
While catalyst is using activity, the quantity for needing to carry out presulfurization processing can be reduced to a certain extent and carries sulfur content.
Description of the drawings
Fig. 1 is the principle process schematic diagram of the method for the present invention.Wherein whole protective agents have been each formed as ex situ presulfiding type.
Specific implementation mode
Below in conjunction with the accompanying drawings, come illustrate the present invention start-up vulcanization method.
As shown in Figure 1, a kind of embodiment of the hydrogenation catalyst start-up method of the present invention is as follows：
According to gas flow direction, recycle hydrogen 1 is lived by containing all ex situ presulfiding type hydrogenation protecting agent 2 and two classes
The hydrofining reactor 4 of property center hydrotreating catalyst 3, obtains effluent 5；Again by containing hydrocracking catalyst 6
And it is hydrocracked the hydrocracking reactor 8 of post-processing catalyst 7, effluent 9 enters in high-pressure separator 10.Top is discharged
Gas phase 11 by after circulating hydrogen compressor 12 with supplement hydrogen 13 mix, obtain recycle hydrogen 1.Technique stream is got through according to above-mentioned steps
Cheng Hou is gradually increased the inlet temperature of hydrofining reactor 4 to 200 DEG C, by cold hydrogen, controls its underpart hydrorefining catalyst
The inlet temperature of agent bed is 160 DEG C, and a small amount of anhydrous liquid ammonia 15, constant temperature are injected into system.Wait for hydrofining reactor
It exports after concentration of hydrogen sulfide is more than or equal to 100 μ L/L, then adjusts the inlet temperature of hydrofining reactor to 180 DEG C, according to normal
The rule gas phase mode of going into operation carries out follow-up start-up process, and the water 14 generated in sulfidation is arranged by 10 bottom of high-pressure separator
Go out.
The start-up vulcanization method of the present invention is further described followed by specific embodiment.
The property of the protective agent and catalyst that are used in embodiment 1 and Comparative Examples 1 and 2 is listed in table 1.It is Fushun oil
The commodity protective agent and catalyst of chemical research institute's development and production, wherein embodiment 1 are start-up method of the present invention, using above-mentioned reality
Mode is applied, in solution formulation, the outer protectant loadings of presulfurization of adjuster is answered and carries sulfur content, its excessive sulfur content is made to reach
25% or more of sulfur content is needed to two class site catalyst theories, comparative example 1 is conventional dry start-up process, and comparative example 2 is normal
Advise wet method start-up process.
The main physico-chemical property of 1 catalyst of table.
Embodiment 1
After the airtight qualification of hydrocracking unit hydrogen, reaction system inlet pressure is adjusted to 14.0MPa, system circulation hydrogen
Amount is that 70% full dose recycles.Starting to heat up with 20 DEG C/h, when rising to 200 DEG C, the inlet temperature of the second bed of control is 160 DEG C, and
Anhydrous liquid ammonia about 50kg/h is injected, after constant temperature waits for the concentration of hydrogen sulfide of hydrotreating reactor outlet to reach 0.01v%, it is believed that
Hydrogen sulfide forms hydrotreating catalyst and protects.Then adjustment reactor inlet temperature is 180 DEG C, starts injection vulcanization
Agent DMDS, after the concentration of hydrogen sulfide of hydrocracking reactor outlet reaches 0.1v%, adjustment reaction bed temperature is 230 DEG C,
Constant temperature 8 hours, it is 5000 μ L/L that this process maintains concentration of hydrogen sulfide in recycle hydrogen by adjusting vulcanizing agent injection rate；Adjustment catalysis
Agent bed temperature is 290 DEG C, and constant temperature 2 hours, this process maintains concentration of hydrogen sulfide in recycle hydrogen by adjusting vulcanizing agent injection rate
For 8000 μ L/L；Continue that reaction bed temperature is warming up to 370 DEG C with 8 DEG C/h, constant temperature 8 hours, the process is by adjusting sulphur
It is 15000 μ L/L that agent injection rate, which maintains concentration of hydrogen sulfide in recycle hydrogen, and catalyst vulcanization terminates, in entire sulfidation, control
Hydrogen purity in recycle hydrogen processed is more than 80 v%.After vulcanization, reaction bed temperature is down to 150 DEG C, and according to conventional dry
The method pattern that goes into operation carries out the introducing of low nitrogen oil, the passivation of note ammonia and switching feedstock oil operation, after steady running 500 hours, sample into
Row analysis.
Comparative example 1
Dry method is carried out according to the vulcanization process of this field conventional high-pressure hydrocracking unit to go into operation, vulcanizing agent used is
DMDS.Detailed process is：After the airtight qualification of hydrocracking unit hydrogen, reaction system inlet pressure is adjusted to 14.0MPa, is opened
Begin to heat up with 20 DEG C/h, when rising to 180 DEG C, start to inject vulcanizing agent DMDS, waits for that the hydrogen sulfide of hydrocracking reactor outlet is dense
After degree reaches 0.1v%, adjustment reaction bed temperature is 230 DEG C, and constant temperature 8 hours, this process is by adjusting vulcanizing agent injection rate
It is 5000 μ L/L to maintain concentration of hydrogen sulfide in recycle hydrogen；It is 290 DEG C to adjust reaction bed temperature, constant temperature 2 hours, this process is logical
It is 8000 μ L/L to cross adjustment vulcanizing agent injection rate and maintain concentration of hydrogen sulfide in recycle hydrogen；Continue catalyst bed temperature with 8 DEG C/h
Degree is warming up to 370 DEG C, constant temperature 8 hours, which maintains the concentration of hydrogen sulfide in recycle hydrogen to be by adjusting vulcanizing agent injection rate
15000 μ L/L, catalyst vulcanization terminate, and in entire sulfidation, the hydrogen purity in control loop hydrogen is more than 80 v%.Vulcanization knot
Reaction bed temperature is down to 150 DEG C by Shu Hou, and carries out the introducing of low nitrogen oil according to the conventional dry pattern that goes into operation, and note ammonia is blunt
Change and switching feedstock oil operation, after steady running 500 hours, sampling is analyzed.
Comparative example 2
Wet method is carried out according to the vulcanization process of this field conventional high-pressure hydrocracking unit to go into operation, vulcanizing agent used is
DMDS.Detailed process is：After the airtight qualification of hydrocracking unit hydrogen, reaction system inlet pressure is adjusted to 14.0MPa, is drawn
Enter low nitrogen to go into operation oil, then be heated up with 20 DEG C/h, when rising to 180 DEG C, starts note sulphur pump, vulcanizing agent is injected into reaction system
In.After the concentration of hydrogen sulfide of hydrocracking reactor outlet reaches 0.1v%, it is believed that hydrogen sulfide has penetrated catalyst bed.Adjustment
Reaction bed temperature is 230 DEG C, and constant temperature 8 hours, this process is by adjusting hydrogen sulfide in vulcanizing agent the controlling of injecting quantity recycle hydrogen
A concentration of 5000 μ L/L；Anhydrous liquid ammonia and demineralized water are injected, after ammonia density is up to 0.1% in high score acid water, it is believed that ammonia has been worn
Thoroughly, and the charge velocity of anhydrous liquid ammonia is adjusted, it is 0.8% to maintain ammonia density, and it is 290 DEG C then to adjust reaction bed temperature, permanent
Temperature 2 hours, this process are 8000 μ L/L by adjusting concentration of hydrogen sulfide in vulcanizing agent the controlling of injecting quantity recycle hydrogen；Continue with 6 DEG C/
Reaction bed temperature is warming up to 320 DEG C by h, and constant temperature 4 hours, this process is by adjusting in vulcanizing agent the controlling of injecting quantity recycle hydrogen
Concentration of hydrogen sulfide is 15000 μ L/L, and catalyst vulcanization terminates, and in entire sulfidation, the hydrogen purity in control loop hydrogen is more than
80 v%.After vulcanization, switching feedstock oil is operated, and after steady running 500 hours, sampling is analyzed
Embodiment 1 and Comparative Examples 1 and 2, processed feedstock property and used catalyst all same, sulfidation are mainly joined
Number is shown in Table 2, and feedstock property is shown in Table 3, and process conditions and reactivity are shown in Table 4.
2 sulfidation major parameter of table.
3 raw material oil nature of table.
4 reaction condition of table.
Can be seen that the maximum feature of start-up method of the present invention from above embodiment is, passes through the tune in process conditions
The hydrogen sulfide that whole and grading ex situ presulfiding type protective agent decomposes is protected catalyst in chilling process and is aided with auxiliary in advance
Gas is helped, the purpose of gas-phase presulfiding may be implemented, reaches and avoids catalyst hair of coking and overheating problem in start-up process
It is raw, while catalyst can be made uniformly to vulcanize, strengthen the degree of vulcanization in booster, improves its reactivity, and reduce examination
The consumption of agent.It is without any changes using enterprise's existing apparatus for some drawbacks present in existing start-up method, only
The purpose for improving catalyst activity is realized by the variation of combination, optimizes the product distribution and product matter of hydrocracking unit
Amount, has found an economy, feasible approach, while reducing the discharge capacity of start-up process exhaust gas, waste water.Long-range sees, energy
The whole investment for enough reducing device, has prodigious advantage, development prospect wide on human and material resources.
Claims (14)
1. a kind of start-up method for the hydrocracking unit containing two class active hydrofining catalysts, including following content：
a）Hydrocracking unit includes hydrofining reactor and hydrocracking reactor, according to the direction of logistics, hydrofinishing
Reactor loads hydrogenation protecting agent and hydrotreating catalyst successively from top to bottom；Hydrocracking reactor fills successively from top to bottom
Fill out hydrocracking catalyst and plus hydrogen post-processing catalyst；Wherein hydrogenation protecting agent is ex situ presulfiding catalyst, hydrotreating
Catalyst is two class activated centre hydrogenation catalysts；
b）By hydrocracking unit operating mode according to the conventional pattern setting that goes into operation, and step up hydrofining reactor inlet temperature
It to 180~200 DEG C, is adjusted by cold hydrogen, control hydrofining reactor includes two class activated centre hydrogenation catalyst beds
Inlet temperature is not higher than 160 DEG C；
c）Constant temperature, after hydrofining reactor exports concentration of hydrogen sulfide qualification, adjustment hydrofining reactor inlet temperature is
170 DEG C~190 DEG C, and stop the injection of cold hydrogen；
d）As step c）After the completion, vulcanizing agent is injected to reaction system, then according to conventional gas-phase presulfiding method to catalyst
It goes into operation；
Wherein, step c）The concentration of hydrogen sulfide qualification refers to that concentration of hydrogen sulfide is 100 μ L/L or more.
2. according to the method for claim 1, which is characterized in that with the stereometer of catalyst, the hydrogenation catalyst that is loaded,
Hydrotreating catalyst, hydrocracking catalyst and be hydrocracked the volume fraction of post-processing catalyst be respectively 4%~10%,
30%~60%, 35%~55% and 4%~10%.
3. according to the method for claim 1, which is characterized in that in the hydrogenation protecting agent, sulphur auxiliary agent is in terms of elementary sulfur
Weight content be 5%~25%.
4. according to the method for claim 3, which is characterized in that the hydrogenation protecting agent is with VI B races and/or the VIIIth race gold
It is active component to belong to, using aluminium oxide or silicon-containing alumina as carrier, on the basis of the weight of catalyst, and group VIB tenor
It is calculated as 0wt%~10wt% with oxide, group VIII metal content is calculated as the wt% of 0wt%~8 with oxide.
5. according to the method for claim 4, which is characterized in that group VIB metal is Mo and/or W, group VIII metal Co
And/or Ni.
6. according to the method for claim 1, which is characterized in that described containing contains in two class activated centre hydrogenation catalysts
Organic additive, organic additive are any substance that complex reaction occurs with molybdenum and/or tungsten, the content of organic additive in the catalyst
For 1~10 wt% of the total metal contents in soil in terms of oxide.
7. according to the method for claim 6, which is characterized in that the organic additive be selected from citric acid, methylethanolamine,
One or more of ehtylethanolamine, dimethylethanolamine.
8. according to the method for claim 1, which is characterized in that step b）The routine goes into operation the reactor operating mode of pattern
Including：System circulation hydrogen amount recycles for 50~100% full doses, and reactor inlet pressure is 90~100% design pressures, and reactor enters
Mouth temperature is not higher than 160 DEG C, and heating rate is not higher than 20 DEG C/h.
9. according to the method for claim 1, which is characterized in that step c）The constant temperature time is 4~8 hours.
10. according to the method for claim 1, which is characterized in that step d）The operating condition of the gas-phase presulfiding method is：
5.0~16.0 MPa of reaction pressure, hydrogen circulation amount recycle for 50%~100% full dose, and curing temperature section is 100 DEG C~380
℃。
11. according to the method for claim 6, which is characterized in that in step b）In be optionally injected into auxiliary protection gas, institute
The auxiliary protection gas stated is hydrogen sulfide or anhydrous liquid ammonia.
12. according to the method for claim 11, which is characterized in that the organic additive is alkalescent substance, and auxiliary is protected
Shield gas is hydrogen sulfide.
13. according to the method for claim 11, which is characterized in that the organic additive is acidulous material, and auxiliary is protected
Shield gas is anhydrous liquid ammonia.
14. according to the method for claim 3, which is characterized in that the sulphur auxiliary agent is selected from elemental sulfur, mercaptan, more vulcanizations
Ammonium and combinations thereof.
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| CN109777483B (en) * | 2017-11-14 | 2020-12-08 | 中国石油化工股份有限公司 | Method for stabilizing quality of hydrocracking product |
| CN109777485B (en) * | 2017-11-14 | 2020-12-08 | 中国石油化工股份有限公司 | Method for improving quality of hydrocracking product |
| CN111378476B (en) * | 2018-12-31 | 2021-01-05 | 中国石油化工股份有限公司 | Startup preparation method of hydrocracking device |
| CN111378473B (en) * | 2018-12-31 | 2021-01-05 | 中国石油化工股份有限公司 | Startup preparation method of hydrofining device |
| CN111378475B (en) * | 2018-12-31 | 2021-02-05 | 中国石油化工股份有限公司 | Startup activation preparation method of hydrocracking device |
| CN111378481B (en) * | 2018-12-31 | 2021-02-05 | 中国石油化工股份有限公司 | Startup preparation method of hydro-upgrading device |
| CN111378480B (en) * | 2018-12-31 | 2021-02-05 | 中国石油化工股份有限公司 | Startup preparation method of hydro-upgrading device |
| CN111378478B (en) * | 2018-12-31 | 2021-02-05 | 中国石油化工股份有限公司 | Method for preparing for starting up hydrotreater |
| CN111378479B (en) * | 2018-12-31 | 2021-02-05 | 中国石油化工股份有限公司 | Startup preparation method of hydrotreatment device |
| CN111378477B (en) * | 2018-12-31 | 2021-01-05 | 中国石油化工股份有限公司 | Startup preparation method of hydrocracking device |
| CN111378482B (en) * | 2018-12-31 | 2021-01-05 | 中国石油化工股份有限公司 | Start-up activation preparation method of hydrocracking device |
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