CN109777482A - A method of extending hydrocracked product quality stability - Google Patents
A method of extending hydrocracked product quality stability Download PDFInfo
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- CN109777482A CN109777482A CN201711118843.1A CN201711118843A CN109777482A CN 109777482 A CN109777482 A CN 109777482A CN 201711118843 A CN201711118843 A CN 201711118843A CN 109777482 A CN109777482 A CN 109777482A
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Abstract
The present invention discloses a kind of method for extending hydrocracked product quality stability, including following content: hydrocracking raw material enters after mixing with hydrogen is hydrocracked preatreating reactors progress refining reaction, reaction effluent, which enters, carries out hydrocracking reaction in hydrocracking reactor, four hydrocracking catalyst beds are set in the hydrocracking reactor, it is respectively provided at the top and bottom of any hydrocracking reactor bed when the conversion ratio for being greater than 350 DEG C of fractions in hydrocracking raw material is 90 ~ 99% and adds hydrogen post-processing catalyst bed, post-processing catalyst volume ratio along the filling of logistics direction is 3-7:5-15:5-25:20-40:30-50, volume of loaded in the hydrocracking reactor plus hydrogen post-processing catalyst with the hydrocracking catalyst loaded in hydrocracking reactor Than for 1:6 ~ 8, isocrackate obtains various products after separation.This method can significantly improve the stability of hydrocracked product.
Description
Technical field
The present invention relates to a kind of methods for extending hydrocracked product quality stability, relate in particular to a kind of extension length
The method of heavy naphtha product quality stability in period run process middle and later periods hydrocracked product.
Background technique
Hydrocracking process be under the action of facing hydrogen, high temperature, condition of high voltage and catalyst, make heavy distillate (VGO,
CGO, DAO) hydrodesulfurization, hydrodenitrogeneration, polycyclic aromatic hydrocarbon add hydrogen to be saturated and open loop cracking, it is converted into light oil and intermediate oil etc.
The process of purpose product has the characteristics that flexible operation, product quality are good, environmental-friendly, as heavy distillate deep processing
One of main technique, it is not only the important means of petroleum refining industry's production light-end products, and also becomes petrochemical industry enterprise
The key technology of industry plays the not replaceable effect of other techniques, it has also become the standard configuration of current major oil refining enterprise, it is right
" oil is changed, is fine " of full factory combines and crucial effect is played in process optimization configuration.
Standard configuration device of the hydrocracking unit as oil refining enterprise, plays between oil refining-oil refining and oil refining-chemical industry
Critical linking over effect, liquid product light naphthar can be used as gasoline blend component production premium, scheelite brain
Oil can be used as catalytic reforming units charging production Reformed Gasoline or aromatic hydrocarbon product, kerosene can be used as aviation kerosine or low solidifying bavin
Oil product, diesel oil can be used as high-grade fuel oil product, tail oil can be used as lube oil base stocks or ethylene cracking material, and according to
The yield and quality of each liquid product can be adjusted flexibly in the difference of the catalyst and process conditions that use, so it is flexibly
Property and quality are self-evident.
The difference that current country's hydrocracking unit is balanced according to enterprise's oil product in actual use, purpose product or life
Production mode is different, but in order to cater to the demand in market, pursues higher economic benefit, adjustment modes are consistent on the whole
Property is stronger.Domestic market diesel product is superfluous, and market is obstructed, so improving diesel and gasoline ratio, reduces production of diesel oil and has become and work as
Preceding or even oil refining enterprise's optimization and upgrading in recent years basic goal.Diesel and gasoline ratio is reduced, although approaches and methods are not single,
The yield on the one hand needing to reduce diesel oil on the whole, on the other hand needs to increase the yield of gasoline, for hydrocracking unit
For, it being capable of the spirit between production gasoline and production diesel oil both of which by the change of technique, operating condition and catalyst
Switching living under current production status, under the premise of guaranteeing that other products are qualified, improves vapour for selected catalyst
Oil yield also has become main productive target, will definitely increase the conversion level of reaction process in this way, increases operational severe
Scale causes reaction temperature and conversion ratio higher.
Simultaneously a variety of reactions occur for hydrocracking process.Cracking reaction generally includes carbon-to-carbon singly-bound and is fractured into compared with low molecule
Measure compound, including the aromatic side chain fracture of alkene and high-molecular weight compounds.Also occur in hydrocracking unit plus hydrogen is anti-
It answers, the double-bond hydrogenation including aromatic hydrocarbons and olefin(e) compound.So existing containing hydrogenation process while with dehydrogenation in reaction process
Process, under different reaction operating conditions, the equilibrium constant has a certain difference the two, and the alkene generated in reaction process is unfavorable for
The stability of subsequent product, therefore general hydrocracking process always increases a certain amount of purification in the bottommost of cracker
Catalyst had both been post-processing catalyst, and effect can carry out the alkene generated in reaction process plus hydrogen saturation, to increase
The stability of subsequent product and the tendency for reducing generation mercaptan, such as can be to avoid mercaptan in heavy naphtha and boat product of coal
It is exceeded, to guarantee qualified product, or avoid heavy naphtha alkene exceeded, i.e., bromine index is exceeded to accelerating to reform
The deactivation rate of catalyst.
CN200610047864.4 describes a kind of one-stage serial hydrocracking method, is hydrocracked pre- place in one section of series winding
It manages and loads pretreatment catalyst and hydrocracking catalyst in reactor, hydrocracking catalyst is loaded in hydrocracking reactor
Agent and plus hydrogen post-processing catalyst.Compared with prior art, the overall activity of hydrocracking unit can be improved in the method for the present invention,
The processing capacity of device can be increased or increase operation cycle, while product quality can be improved.CN200780020520.7
A kind of method for hydrogen cracking for producing low-sulfur diesel-oil is described, is reacted in single hop or two-stage reforming, catalysis is passed through
After the optimization of agent is promoted and carries out reasonable sanding to reaction process, the production of low-sulfur diesel-oil may be implemented.But both for being related to
To being hydrocracked, post-processing reaction zone temperature is excessively high, and catalyst activity is not extremely to match, unstable product quality, especially instead
The phenomenon for answering middle and later periods problem more serious.
CN201510604895.4 describes a kind of preparation method of post-processing type hydrocracking catalyst, by catalysis
The optimization of agent preparation process limits the production that hydrogenation activity and the higher product of selectivity may be implemented, product intermediate oil
Selectivity it is higher, be suitble to the hydrocracking catalyst of processing various different metals composition.But it still falls within be hydrocracked in principle
Catalyst scope, if being used as plus hydrogen post-processes, the stability of product quality is difficult to ensure, after short-run, i.e., can
There is the problem that olefin(e) centent is exceeded or mercaptan is exceeded in liquid-phase product.
CN02144950.3 describes one kind and is hydrocracked post-processing catalyst and preparation method thereof, by catalyst
Preparation improves, and hydro-sweetening, alkene saturated activity height may be implemented, and the good feature of stability is particularly suitable for being hydrocracked
Post-processing production low thioalcohol product process.Although it improves to some extent to the preparation process of catalyst, but not actual with post-processing
It reacts operating condition to be adapted, however it remains reaction middle and later periods product quality is difficult to stable feature, furthermore also not to the acid of catalyst
The critical index such as property make annotation, are not directed to the improvement etc. of Hydrogenation and cracking performance, and when practical application can still deposit
In problem.
CN02144949.X describes a kind of hydrotreating catalyst and preparation method thereof, by catalyst preparation process
Improvement, may be implemented compared with prior art, the high feature of hydro-sweetening, alkene saturated activity, be particularly suitable for plus hydrogen
Cracking post-processes removal of mercaptans sulphur process.It still falls within catalyst related patents in principle, is not defined modification to technical process,
Do not achieve the purpose that catalyst preparation is complete unified with technique application control, can not thoroughly realize the optimization of product quality, this
Outer its improves preparation method and is not optimized to some key parameters, when application can certainly will also exist reaction temperature it is excessively high after,
Catalyst deactivation rate is accelerated, and severity increases in addition, to cause the appearance of individual product quality dissatisfaction situation.
Summary of the invention
For in the prior art, the alkene that the hydrocracking reaction process middle and later periods of post-processing catalyst is generally existing is used
Exceeded, i.e., the problems such as heavy naphtha bromine index is higher, mercaptan is higher and boat product of coal sulphur is exceeded, the present invention is by catalyst
Gradation uses and temperature control provides a kind of method for improving hydrocracked product quality stability.
A method of improving hydrocracked product quality, including following content: after hydrocracking raw material is mixed with hydrogen
Refining reaction is carried out into preatreating reactors is hydrocracked, reaction effluent, which enters in hydrocracking reactor, carries out that hydrogen is added to split
Change reaction, four hydrocracking catalyst beds are set in the hydrocracking reactor, when being greater than 350 in hydrocracking raw material
The conversion ratio of DEG C fraction be respectively provided at the top and bottom of any hydrocracking reactor bed when being 90 ~ 99% plus hydrogen after
Catalyst bed is managed, the post-processing catalyst volume ratio along the filling of logistics direction is 3-7:5-15:5-25:20-40:30-50,
Loading in hydrocracking reactor plus hydrogen post-processing catalyst (total) is hydrocracked with what is loaded in hydrocracking reactor
The volume ratio of catalyst (total) is 1:6 ~ 8, and isocrackate obtains various products after separation.
In the method for the present invention, preferably at least in the middle and later periods of device operating, (middle and later periods of described device operating is generally referred to
After going into operation operation 12 months, according to the difference of used hydrocracking catalyst type, the time is had a certain difference)
Control the hydrotreating reaction temperature of filling plus hydrogen post-processing catalyst between the bed of any hydrocracking catalyst compare and its
The reaction temperature of adjacent upper hydrocracking catalyst bed is 5 ~ 19 DEG C low, and preferably 6 ~ 18 DEG C.
The method of the present invention, between the bed plus the control of hydrogen post-processing catalyst temperature is real by way of injecting cold hydrogen
It is existing so that the reaction product under overhead stream touches temperature at first in this bed reduce after plus hydrogen post-processing catalyst, this
Sample can further decrease the olefin(e) centent in reactant to greatest extent, mitigate the hydrogenation pressure of subsequent post-processing catalyst.
According to the difference of molecular sieve quality content in hydrocracking catalyst, the amplitude to cool down also different from is controlled.Generally, when
When molecular sieve quality content < 20%, the hydrotreating reaction temperature of filling plus hydrogen post-processing catalyst between the bed of logistics direction
Reaction temperature cooling extent compared to upper hydrocracking catalyst bed adjacent thereto is respectively 7 ~ 11 DEG C, 7 ~ 11 DEG C, 8 ~
12℃；When molecular sieve quality content 20 ~ 50%, filling plus the hydrotreating of hydrogen post-processing catalyst between the bed of logistics direction
Reaction temperature compared to the reaction temperature cooling extent of upper hydrocracking catalyst bed adjacent thereto is respectively 10 ~ 13 DEG C,
10~13℃,12~15℃；As molecular sieve quality content > 50%, filling plus hydrogen post-processing catalyst between the bed of logistics direction
Hydrotreating reaction temperature compared to upper hydrocracking catalyst bed adjacent thereto reaction temperature cooling extent distinguish
It is 12 ~ 15 DEG C, 12 ~ 15 DEG C, 15 ~ 18 DEG C.No matter using the hydrocracking catalyst of which kind of molecular sieve content, it is necessary to be provided simultaneously with
The means to cool down at the top of hydrocracking reactor head bed, according to the difference of control mode, cooling extent can be 3 ~ 25 DEG C, excellent
Select 5 ~ 20 DEG C.
It needs exist for further illustrating, using the hydrocracking catalyst of different molecular sieve content, control identical
When reaction depth, average reaction temperature is had differences, when molecular sieve content is lower (< 20%), the means that cool down and cooling
Amplitude great achievement is first choice, and when molecular sieve content is higher (> 50%), control hydrocracking reactor bottom adds hydrogen to post-process air speed
And ratio great achievement is first choice.
In the method for the present invention, the positional relationship of stream flow direction definition catalyst bed is pressed in hydrocracking reactor,
It is known as the first catalyst bed with the catalyst bed that logistics contacts at first.
In the method for the present invention, the hydrocracking raw material can be wax oil raw material either diesel raw material etc., as long as can
Routinely to be fed as hydrocracking unit, but preferably wax oil raw material, particularly heavy wax oil raw material.Its boiling range is general
For 250 DEG C~600 DEG C, do generally 500 DEG C~600 DEG C, preferably 510 DEG C~590 DEG C, nitrogen content in 2500 μ g/g hereinafter,
Generally the 500 μ g/g of μ g/g~2000, sulfur content do not do stringent limitation, and other impurity contents meet custom requirements.It can be with
It is excellent for the wax oil of various straight run or secondary operation etc. that processing naphthene base crude, intermediate base crude or paraffinic base crude oil obtain
The straight-run gas oil component or deasphalted oil of the paraffinic base crude oil of time processing are selected, can be obtained selected from processing paraffinic base crude oil
Various vacuum gas oil (VGO)s (VGO), deasphalted oil (DAO), such as one or more of grand celebration VGO, DAO, long celebrating VGO, DAO.Institute
Stating hydrogen is the charging that common impurity content is met the requirements in industry.
In the method for the present invention, it is as follows to be hydrocracked pretreatment reaction condition: reaction temperature is 300 DEG C~420 DEG C, preferably
310 DEG C~405 DEG C, reaction inlet pressure is 6MPa~16MPa, preferably 8MPa~14MPa；Air speed is 0.5h-1~3.0h-1, excellent
Select 0.6h-1~2.5h-1；Reacting entrance hydrogen to oil volume ratio is 400~1200, preferably 500~1100.
In the method for the present invention, hydrocracking reaction condition is as follows: reaction temperature be 370 DEG C~430 DEG C, preferably 380 DEG C~425
DEG C, operating middle and later periods hydrocracking reaction temperature is 390 DEG C~425 DEG C；Reaction inlet pressure is 6MPa~16MPa, preferably
8MPa~14MPa；Air speed is 0.5h-1~3.0h-1, preferably 0.8h-1~2.8h-1；React entrance hydrogen to oil volume ratio be 400~
1200, preferably 500~1100.
In the method for the present invention, the hydrocracking catalyst includes Cracking Component and hydrogenation component.Cracking Component is usual
Including amorphous silica-alumina and/or molecular sieve, such as Y type, β type or USY molecular sieve.Adhesive is usually aluminium oxide or silica.Add
Hydrogen group is selected from VI race, the metal of VII race or VIII race, metal oxide or metal sulfide, more preferably iron, chromium, molybdenum, tungsten,
Cobalt, nickel or one or more of its sulfide or oxide.On the basis of the weight of catalyst, the content of hydrogenation component is
5%~40%, preferably 10%~35%, molecular sieve content is limited without stringent, but according to the difference of molecular sieve content, the cooling controlled
Amplitude different from.Conventional hydrocracking catalyst can choose existing various commercial catalysts, such as FRIPP is developed
The catalyst such as FC-14, FC-32, FC-46.Also it can according to need specifically to be hydrocracked by the common sense preparation of this field and urge
Agent.
In the method for the present invention, the preatreating reactors that is hydrocracked is filled with pretreating catalyst by hydrocracking.Institute
The pretreating catalyst by hydrocracking stated includes carrier and the hydrogenation metal that is loaded, on the basis of the weight of catalyst, usually
Including metal component of group VIB in the periodic table of elements, if tungsten and/or molybdenum are calculated as 10%~35% with oxide, preferably 15%~
30%；Group VIII metal such as nickel and/or cobalt are calculated as 1%~7%, preferably 1.5%~6% with oxide.Carrier is inorganic refractory oxidation
Object is selected generally from aluminium oxide, amorphous silicon aluminium, silica, titanium oxide etc..The preferred metal of such catalyst is Mo-Ni, compares table
Area ≮ 160m2/g-1, Kong Rong ≮ 0.3ml/g-1, infrared total acid 0.4mmol/g~0.7mmol/g, wherein conventional hydrocracking pre-
Processing catalyst can choose existing various commercial catalysts, such as Fushun Petrochemical Research Institute (FRIPP) develops
3936,3996, the hydrotreating catalysts such as FF-16, FF-26, FF-36, FF-46；Also it can according to need by this field
It is prepared by common sense.The refining reaction is the process of the impurity removals such as desulfurization, denitrogenation, aromatic hydrocarbons saturation.
In the method for the present invention, hydrogen post-processing catalyst is added to add for modified between bed in the hydrocracking reactor
Additive modification can be added by it to be prepared in hydrogen cracking pretreatment catalyst, and component mainly includes carrier and loaded
Hydrogenation metal generally include metal component of group VIB in the periodic table of elements on the basis of the weight of catalyst, such as tungsten and/or
Molybdenum is calculated as 5%~25%, preferably 10%~20% with oxide；Group VIII metal such as nickel and/or cobalt are calculated as 1%~5% with oxide,
Preferably 1.5%~4%.Carrier is inorganic refractory oxide, is selected generally from aluminium oxide, amorphous silicon aluminium, silica, titanium oxide
Deng.The preferred metal of such catalyst is Mo-Co, specific surface area ≮ 180m2/g-1, Kong Rong ≮ 0.4ml/g-1, infrared total acid <
0.2mmol/g, hydrogenation active component mass content and meleic acid acid amount be respectively lower than pretreating catalyst by hydrocracking 5 ~
85%, 50 ~ 95%, preferably 10 ~ 65%, 55 ~ 85%.The hydrocracking reactor bottom adds hydrogen post-processing catalyst can be used
Above-mentioned pretreating catalyst by hydrocracking or modified pretreating catalyst by hydrocracking.
Control method according to the present invention, subsequent product separation, fractional distillation process and the various qualified products are
The conventional understanding of those skilled in the art, does not do tired state herein.
Compared with prior art, the present invention, which is hydrocracked to have used at the top of bed, adds hydrogen post-processing catalyst, adds with conventional
Hydrogen cracking pretreatment catalyst is compared, since it uses position and the difference of reaction purpose, it is not necessary to pursue excessively high denitrogenation
Can, therefore its acid and Hydrogenation is reduced, delay the tendency of catalyst coking and deactivation in operational process, especially in high temperature
The deactivation rate of conversion zone maintains the stability of Hydrogenation, can reduce the alkene generated in reaction process to greatest extent
Deng unsaturated hydro carbons, also comprising unsaturated hydrocarbons such as alkene for being generated during weighted BMO spaces, from reaction angle by it as far as possible
Conversion avoids subsequent react with hydrogen sulfide from generating mercaptan sulfur or be directly entered in product, has to improvement and stabilized product quality
Play the role of very big.
The present invention utilizes the fusion of the difference of hydrocracking process differential responses area potential temperature and the means that cool down, by bed top
Portion adds the reaction condition of hydrogen post-processing catalyst to carry out temperature optimization adjustment, adds hydrogen to post-process high-temperature section by raw material it
It is transferred to the low-temp reaction section of temperature-controllable, is on the one hand largely satisfied in low-temperature space to the alkene that top reaction process generates in this way
With addition to get rid of, the reaction severity of bottom post-processing catalyst is reduced, its reaction process has on the other hand been delayed
Coking tendency and deactivation rate, to strengthen the stability of hydrocracking unit operating, especially middle and later periods heavy naphtha
And the quality stability of boat product of coal, it can further extend the cycle of operation of device in this way, be reduced for enterprise unplanned
The loss of shut-down bring.
The present invention improves the preparation of catalyst and the reasonable application of process conditions has carried out perfect fusion, not right
Under the premise of hydrocracking unit carries out any transformation, only by the grading loading of catalyst, type change and condition optimizing, just
It may be implemented to improve product quality, especially operate the purpose of middle and later periods product quality, and by different conversion levels and catalysis
The improvement of agent bed has carried out reasonable correspondence, reduces the complexity of transformation, has reached maximum value with the smallest change.
It can thoroughly solve under current market demand, the variation of device technique condition, product demand change are to product quality and product week
It is influenced caused by phase, enhances oil refining enterprise for the reply mobile type and stability of turn of the market, invested not in human and material resources
Under the premise of change, very considerable economic benefit and social benefit, application advantage can be brought very significant.
Result of study shows that conventional post-processing catalyst is exactly the bottom for being seated in Cracking catalyst bed, effect
The alkene generated in reaction process is exactly reduced, but since reaction temperature herein is higher, substantially belongs to entire hydrogenation reaction
The highest potential temperature of process, so dehydrogenation reaction odds also can be big during being saturated to alkene, and with operating week
The extension of phase, reaction temperature can be higher and higher, until regular occur that heavy naphtha bromine index is exceeded to ask when the reaction middle and later periods
Topic, for certain low activity hydrocracking catalysts, problem is more serious, and current fuel oil market has already mentioned above
The demand of field causes no matter urge due to high heavy naphtha demand even with high-activity hydrocracking using which kind of catalyst
Agent, reaction temperature is also relatively high, and still more if catalyst activity reduces, reaction temperature can be increased further,
Problems are present not only in middle-pressure hydrocracker, are frequently occurred in high-pressure hydrocracking device.So
Heavy naphtha bromine index is higher, exceeded to have become current oil refining enterprise's hydrocracking unit middle and later periods more serious for boat product of coal mercaptan
The problem of, it would be highly desirable to it solves.The method of the present invention for drawback present on post-processing catalyst reaction condition, especially in operating after
It, the stage that the decline of catalyst hydrogenation performance, dehydrogenation tendency improve, can using catalyst bed interlayer when phase or high conversion condition
With the means of temperature control, the alkene saturation process under lower potential temperature is set, and with conversion level Proper Match, it is anti-to reduce entire cracking
The content of system internal olefin is answered, while gradation adds hydrogen species catalyst using different performance, so that catalyst performance and technique item
Part more merges, have the characteristics that it is easy to operate, safely controllable, just with implement, can solve operating middle and later periods heavy naphtha bromine
Index, mercaptan is higher and the exceeded problem of boat product of coal mercaptan, not only increases the steady of product quality in device operation process
It is qualitative and extend operation cycle, and do not need to carry out device itself any transformation, only pass through the gradation of catalyst
Change achieves that goal of the invention.
Detailed description of the invention
Fig. 1 is the flow diagram of present invention process method.
Wherein, 1 is feedstock oil, and 2 be hydrogen, and 3 be weighted BMO spaces reactor, and 4 be effluent after pretreatment, and 5 be to add hydrogen
Cracker, 6,7,8,9 and 10 be to add hydrogen post-processing catalyst, and 11 be hydrocracking reaction effluent, and 12 use for cooling
Quenching hydrogen.
Specific embodiment
Combined technical method of the invention is described in detail with reference to the accompanying drawing.It is only listed in process flow in Fig. 1
Core explanation, be omitted some necessary equipment in schematic diagram and container, process be as follows:
Feedstock oil 1 enters weighted BMO spaces reactor 3 with hydrogen 2 after reactor inlet mixes, from top to bottom successively by essence
Effluent 4 is obtained after system reaction, enters back into hydrocracking reactor 5, is obtained after passing sequentially through cracking and refining reaction from top to bottom
Carry out subsequent separation fractional distillation process again to effluent 11；In hydrocracking reactor 5, at the top of the first, second, third and fourth bed
It is filled with and adds hydrogen post-processing catalyst 6,7,8,9, lower part is filled with plus hydrogen post-processing catalyst 10；12 be that can carry out temperature in figure
Spend the quenching hydrogen of control.
A kind of side for improving hydrocracked product quality of the present invention is further illustrated below with reference to Examples and Comparative Examples
The functions and effects of method.The property of feedstock oil used by following Examples and Comparative Examples is shown in Table 1, makes in Examples and Comparative Examples
Catalyst main character is shown in Table 2.
1 feedstock oil main character of table
2 catalyst main character of table
Embodiment and comparative example correspond, and hydrofining reactor and hydrocracking reactor are without any changes, only pass through
The variation of Catalyst packing solves the problems, such as product quality, and the conversion rate of products controlled is consistent, only hydrocracking reactor bed
Layer has differences, and admission space is identical, including Catalyst packing, bed temperature rise (i.e. cooling-down type controllable reaction force down temperature)
Deng.It is the heavy naphtha bromine index situation for operating the middle and later periods that comparative example, which is listed, no matter generally using any content molecular sieve
Catalyst, mid-early stage bromine index are lower.
Embodiment 1
Using process flow shown in FIG. 1, handling catalyst and use A and B, Cracking catalyst uses C1, control reaction mass turns
Rate is 95%, and the duration of runs is 14 months, carries out sampling analysis heavy naphtha bromine index.
Comparative example 1
It using conventional hydrocracking process flow, handles catalyst and uses A and B, Cracking catalyst uses C1, controls reaction mass
Conversion ratio is 95%, and the duration of runs is 14 months, carries out sampling analysis heavy naphtha bromine index.
Embodiment 2
Using process flow shown in FIG. 1, handling catalyst and use A and B, Cracking catalyst uses C2, control reaction mass turns
Rate is 94%, and the duration of runs is 16 months, carries out sampling analysis heavy naphtha bromine index.
Comparative example 2
It using conventional hydrocracking process flow, handles catalyst and uses A and B, Cracking catalyst uses C2, controls reaction mass
Conversion ratio is 94%, and the duration of runs is 16 months, carries out sampling analysis heavy naphtha bromine index.
Embodiment 3
Using process flow shown in FIG. 1, handling catalyst and use A and B, Cracking catalyst uses C3, control reaction mass turns
Rate is 95%, and the duration of runs is 18 months, carries out sampling analysis heavy naphtha bromine index.
Comparative example 3
It using conventional hydrocracking process flow, handles catalyst and uses A and B, Cracking catalyst uses C3, controls reaction mass
Conversion ratio is 95%, and the duration of runs is 18 months, carries out sampling analysis heavy naphtha bromine index.
The effect of above-described embodiment and comparative example is compared, in control same conversion depth (mass transitions rate 95%
When), it is as a result shown in Table 3(as follows and only lists difference cracking bed parameter):
Table 3
The maximum feature that above Examples and Comparative Examples can be seen that the inventive method is under certain reaction operating condition, to add
Hydrogen cracking unit operates the middle and later periods, by the change of the loading position of catalyst with the lower bed inlet temperatures of correspondence, enhancing
The saturability of alkene reaches and improves product quality and stable product quality to reduce the content of alkene in product
Purpose can extend the cycle of operation of device, save the consumption of human and material resources, bring considerable economic benefit and society for enterprise
Meeting benefit, has very big practical application advantage.
Claims (10)
1. a kind of method for extending hydrocracked product quality stability, it is characterised in that: including following content: being hydrocracked original
Material enters after mixing with hydrogen is hydrocracked preatreating reactors progress refining reaction, and reaction effluent enters hydrocracking reaction
Hydrocracking reaction is carried out in device, four hydrocracking catalyst beds are set in the hydrocracking reactor, when adding hydrogen to split
Change and is greater than when the conversion ratio of 350 DEG C of fractions is 90 ~ 99% hydrocracking catalyst in any hydrocracking reactor in raw material
It is respectively provided at the top and bottom of bed and adds hydrogen post-processing catalyst bed, along the post-processing catalyst volume ratio of logistics direction filling
For 3-7:5-15:5-25:20-40:30-50, interior the load plus hydrogen post-processing catalyst of hydrocracking reactor is same to be hydrocracked
The volume ratio of the hydrocracking catalyst loaded in reactor is 1:6 ~ 8, and isocrackate obtains various products after separation.
2. according to the method described in claim 1, being split it is characterized by: at least controlling any plus hydrogen in the middle and later periods of device operating
The hydrotreating reaction temperature of filling plus hydrogen post-processing catalyst is compared to upper one plus hydrogen adjacent thereto between changing the bed of catalyst
The reaction temperature of Cracking catalyst bed is 5 ~ 19 DEG C low.
3. according to the method described in claim 1, it is characterized by: as molecular sieve quality content < in hydrocracking catalyst
When 20%, the hydrotreating reaction temperature of filling plus hydrogen post-processing catalyst is upper compared to adjacent thereto between the bed of logistics direction
The reaction temperature cooling extent of one hydrocracking catalyst bed is respectively 7 ~ 11 DEG C, 7 ~ 11 DEG C, 8 ~ 12 DEG C；It is urged when being hydrocracked
In agent when molecular sieve quality content 20 ~ 50%, filling plus the hydrotreating of hydrogen post-processing catalyst are anti-between the bed of logistics direction
To answer temperature compared to the reaction temperature cooling extent of upper hydrocracking catalyst bed adjacent thereto be respectively 10 ~ 13 DEG C, 10 ~
13℃,12~15℃；As molecular sieve quality content > 50% in hydrocracking catalyst, filling plus hydrogen between the bed of logistics direction
The hydrotreating reaction temperature of post-processing catalyst compares the reaction temperature of upper hydrocracking catalyst bed adjacent thereto
Cooling extent is respectively 12 ~ 15 DEG C, 12 ~ 15 DEG C, 15 ~ 18 DEG C.
4. according to the method described in claim 1, it is characterized by: the hydrocracking raw material is wax oil raw material or diesel oil
Raw material.
5. according to the method described in claim 1, it is characterized by: to be hydrocracked pretreatment reaction condition as follows: reaction temperature
It is 300 DEG C~420 DEG C；Reaction inlet pressure is 6MPa~16MPa；Air speed is 0.5h-1~3.0h-1；React entrance hydrogen oil volume
Than being 400~1200.
6. according to the method described in claim 1, it is characterized by: the described preatreating reactors that is hydrocracked is filled with plus hydrogen
Cracking pretreatment catalyst, the pretreating catalyst by hydrocracking include carrier and the hydrogenation metal that is loaded, with catalysis
On the basis of the weight of agent, metal component of group VIB is calculated as 10%~35% with oxide；Group VIII metal is calculated as 1% with oxide~
7%, carrier is inorganic refractory oxide.
7. according to the method described in claim 1, it is characterized by: hydrocracking reaction condition is as follows: reaction temperature is 370 DEG C
~430 DEG C, operating middle and later periods hydrocracking reaction temperature is 390 DEG C~425 DEG C；Reaction inlet pressure is 6MPa~16MPa；It is empty
Speed is 0.5h-1~3.0h-1；Reacting entrance hydrogen to oil volume ratio is 400~1200.
8. according to the method described in claim 1, it is characterized by: the hydrocracking catalyst includes Cracking Component and adds
Hydrogen component, Cracking Component are usually amorphous silica-alumina and/or molecular sieve, hydrogenation component be selected from VI race, VII race or VIII race metal,
Metal oxide or metal sulfide.
9. according to the method described in claim 1, it is characterized by: plus hydrogen post-processing catalyst hydrogenation active component mass content
And meleic acid acid amount is respectively lower than pretreating catalyst by hydrocracking 5 ~ 85%, 50 ~ 95%.
10. according to the method described in claim 1, it is characterized by: adding the temperature control of hydrogen post-processing catalyst between the bed
System is realized by way of injecting cold hydrogen.
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| CN111778067A (en) * | 2020-07-02 | 2020-10-16 | 平顶山学院 | Method for stabilizing quality of hydrocracking product |
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