CN104611053B - High dry point raw material hydrocracking process - Google Patents
High dry point raw material hydrocracking process Download PDFInfo
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- CN104611053B CN104611053B CN201310540550.8A CN201310540550A CN104611053B CN 104611053 B CN104611053 B CN 104611053B CN 201310540550 A CN201310540550 A CN 201310540550A CN 104611053 B CN104611053 B CN 104611053B
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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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention discloses a high dry point raw material hydrocracking process. According to the high dry point raw material hydrocracking process, a high dry point raw material firstly is subjected to a first-stage hydrorefining reaction, and a gas-liquid co-current flow process and a gas-liquid counter flow process are concurrently adopted in the first stage; the generated oil obtained in the first stage enters a second-stage refining stage to carry out a deep denitrogenation and aromatic hydrocarbon saturation reaction, and a gas-liquid co-current flow process is adopted in the second stage; and the second-stage reaction effluent is mixed with supplemental hydrogen gas, and then enters a third-stage reaction zone to carry out a hydrocracking reaction. With the method of the present invention, the nitrogen-containing impurities in the high dry point raw material can be subjected to hydrotreating under the relatively mild condition so as to make the high dry point raw material meet the hydrocracking feeding requirement, such that the hydrocracking raw material source is broadened; and the hydrorefining temperature is substantially reduced so as to increase the operation period of the device and process the poor-quality raw material, or increase the processing capacity of the device in the same operation period.
Description
Technical field
The invention discloses a kind of hydrocracking process, particularly a kind of to process the hydrocracking process that height does raw material.
Background technology
With China's rapid development of economy, PETROLEUM PROCESSING ability rapid growth.At the same time, domestic hydrocracking technology
Large-scale commercial Application is also obtain, by the end of the year 2011, the hydrocracking unit that China is currently running has set more than 40, total to add
Work ability alreadys exceed 50.0Mt/a, and working ability leaps to second place of the world.The increasingly depleted of world's crude resources, international simultaneously
Oil price is hovered in a high position always.2.54 hundred million tons of the imported crude oil altogether of China in 2011, crude oil import dependency degree up to 56.5%,
The healthy, fast-developing of national economy is seriously threatened, makes full use of crude resources to have become the vital task of oil refining industry.
Further, since the variation year by year of domestic crude quality, imported high sulfur crude oil processing capacity is significantly increased, environmental protection to oil refining process and
The requirement of petroleum product-quality is increasingly strict, and market is continuously increased to clean fuel oil and industrial chemicals demand, especially
It is that the high-quality provided as the cleaning intermediate oil of transportation fuel and for devices such as reformation, ethylene feeds, therefore market
Progress to hydrocracking technology level is put forward higher requirement.It is hydrocracked processed wide scope of material, products scheme
Flexibly, liquid product yield is high, can obtain high-quality power fuel and industrial chemicals, and hydrocracking process and technology are increasingly subject to
The most attention of each major oil companies of the world.In order to improve crude oil utilization rate, the yield of high value added product, each great oil refining is improved
Enterprise adopts deep drawing technology, decompressed wax oil to do up to more than 590 DEG C one after another, and even up to 620 DEG C, hydrocracking technology can
This demand is met well.
Hydrocracking process generally can be divided into one-stage process and two-stage method, and wherein one-stage process includes single hop again（Also referred to as single hop one
Agent）Connect with single hop.Mode of operation is broadly divided into circulate operation mode and once-through operation mode.Single stage process is using a kind of
The hydrocracking catalyst of resistance to organic nitrogen, directly by hydrocracking catalyst, technical process is most simple for raw material, operation air speed compared with
Height, but the raw material range processed is narrow, and product Air China coal is second-rate.Single hop is used in series Hydrobon catalyst and is hydrocracked
Catalyst cascade, it is middle without the need for separating, because hydrocracking catalyst used does not have the ability of resistance to organic nitrogen, it is desirable in hydrogenation
Finishing reactor will be the removing of sulfur nitrogen impurity clean, so typically can only operate compared with low-speed.With oil refining enterprise increasingly
Maximize, the large-scale hydrocracking unit of planning construction is more and more, to reach scale and benefit.Single set processing energy of these devices
Power is mostly more than 2,000,000 tons/year.If these large-scale hydrocracking units are using conventional single hop series connection or single stage process technology
By list covering device construction, due to the manufacturing expense and freight of the large equipments such as reactor, raw material pump, heat exchanger it is huge,
Greatly increase will plant construction investment, affect the economic benefit of enterprise；And if building up two covering devices, then will be due to table of equipment
Number is dramatically increased, and equally also will be increased the construction investment of device, and will be increased operating cost.
Existing two-stage reforming technique, such as US3702818 are related to first paragraph raw oil and first pass around hydrofinishing section
Imurity-removal, detached liquid are entered and are hydrocracked section, and first paragraph tail oil enters second segment and continues cracking, and this is conventional two sections and adds
Hydrogen process process.US3549515 first paragraphs use one-stage serial flow process, first paragraph tail oil to enter second segment and continue cracking,
There is the deficiency of above-mentioned one-stage serial technique.US4404088 is related to increase a hydrocracking reaction section, is changing product side
Liquid product yield is improved during case, but flow process is longer.Although these technology schemes are flexibly, technological process is complicated, and investment increases.
CN100526433 is related to first paragraph using two doses of flow processs of single hop, and first paragraph tail oil enters second segment and continues cracking, maximum production
Intermediate oil, is not directed to processing height and does raw material.
The raw oil processed by traditional hydrocracking process does generally less than 530 DEG C.Using crude oil deep vacuum distillation skill
Postoperative, doing for Hydrocracking Raw Oil is significantly improved so that nitrogen content, sulfur content, asphalitine, carbon residue and trace metal impurities
Content substantially increases.It is except because viscosity increase causes raw oil to slow down to the speed that catalytic inner spreads, anti-so as to reduce
Answer outside speed, the non-hydrocarbon compound for also bringing more, structure increasingly complex and polycyclic aromatic hydrocarbon, colloid, asphalitine, a huge sum of money
The impurity such as category, considerably increase hydrogenation difficulty.
The content of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of improved hydrocracking process, for adding
Work height does raw material（Such as deep drawing wax oil）.Compare compared with two-stage reforming technology, technological process is more flexible, can process more
Plus the raw material of poor quality；Compare compared with one-stage serial hydrocracking technology, be greatly improved the working ability of device.
A kind of height of the present invention does raw material hydrocracking process, including herein below：
（1）Under Hydrofinishing conditions, height does raw oil and hydrogen is mixed into first paragraph reaction zone, first paragraph reaction
Area uses Hydrobon catalyst, and the top of first paragraph reaction zone is gas and liquid flowing reaction zone, and cocurrent reaction effluent enters gas
Liquid Disengagement zone is separated, and gas draws reactor；Liquid enters the beds of bottom, the hydrogen introduced with reactor bottom
Gas carries out counter current contacting reaction, and reacted gas leaves reactor from gas-liquid separation zone；The denitrification percent one of first paragraph reaction zone
As be controlled to 60wt% ~ 95wt%；
（2）The generation oil that first paragraph reaction zone obtains enters second segment reaction zone after mixing with hydrogen, carries out deep hydrogenation
Reaction is processed, second segment reaction zone uses Hydrobon catalyst；
（3）The reaction effluent that second segment reaction zone obtains together with hydrogen make-up enter the 3rd section of reaction zone, the 3rd section
Hydrocracking catalyst is used in reaction zone；
（4）The reaction effluent that 3rd section of reaction zone obtains enters separator, obtains gas and liquid；After gas-liquid separation
Gas can be recycled Jing after removing impurities matter, and liquid obtains various hydrocracked products after being directly fractionated into.
In the inventive method, described height does the end point of distillation of raw material（Or do）Generally more than 550 DEG C, preferably
More than 570 DEG C, most preferably 580～620 DEG C.Height does the nitrogen content of raw material typically in 500mg g-1More than.
In the inventive method, the denitrification percent general control of first paragraph reaction zone is 60wt%～95wt%, is preferably controlled to
70wt%～90wt%.In first paragraph reaction zone, the process conditions of cocurrent reaction zone are：Average reaction temperature is 250 ~ 500 DEG C, excellent
Elect 300 ~ 440 DEG C as；Reaction pressure is 5.0 ~ 20.0MPa, preferably 8.0 ~ 17.0MPa；Hydrogen to oil volume ratio is 100:1~4000:
1, preferably 400:1~2000:1；During liquid, volume space velocity is 1.0 ~ 10.0h-1, preferably 1.0 ~ 4.0h-1.In first paragraph reaction zone
The process conditions of counter-flow reaction zone are：Average reaction temperature is 250 ~ 500 DEG C, preferably 300 ~ 440 DEG C；Reaction pressure be 5.0 ~
20.0MPa, preferably 8.0 ~ 17.0MPa；Hydrogen to oil volume ratio is 100:1~2000:1, preferably 400:1~1000:1；Body during liquid
Product air speed is 1.0 ~ 10.0h-1, preferably 1.0 ~ 4.0h-1。
Wherein in step（1）First paragraph reaction zone in, the gas and liquid flowing reaction zone on top and bottom gas-liquid counter current reaction
The hydrodenitrogeneration rate of property and first paragraph that the Catalyst packing volume ratio in area can do raw material according to height specifically determines.
In the inventive method, the process conditions of second segment reaction zone are：Average reaction temperature is 330 ~ 480 DEG C, reaction pressure
Power is 5.0 ~ 20.0MPa, and hydrogen to oil volume ratio is 100:1~4000:1, during liquid, volume space velocity is 0.2 ~ 4.0h-1.Preferred operation bar
Part is：Average reaction temperature is 350 ~ 450 DEG C, and reaction pressure is 8.0 ~ 17.0MPa, and hydrogen to oil volume ratio is 400:1~2000:1,
During liquid, volume space velocity is 0.5 ~ 3.0h-1。
In the inventive method, the process conditions that the 3rd section of reaction zone is hydrocracked are：Average reaction temperature is 250 ~ 500
DEG C, preferably 300 ~ 440 DEG C；Reaction pressure is 5.0 ~ 20.0MPa, preferably 8.0 ~ 17.0MPa；Hydrogen to oil volume ratio is 100:1~
4000:1, preferably 400:1~2000:1；During liquid, volume space velocity is 1.0 ~ 10.0h-1, preferably 1.0 ~ 4.0h-1。
In the inventive method, according to unit scale, first paragraph reaction zone can arrange one or several reactors, second segment
Reaction zone can also arrange one or several reactors, and the 3rd section of reaction zone typically arranges a reactor.
In the inventive method, the gas phase that first paragraph reaction zone gas-liquid separation zone obtains can be followed Jing after removing hydrogen sulfide and ammonia
Ring is used, and liquid phase enters second segment reaction zone.Second segment reaction zone reaction effluent carries out hydrogenation into the 3rd section of reaction zone and splits
Change reaction.3rd section of reaction effluent carries out gas-liquid separation first, and gas phase removal hydrogen sulfide and ammonia Posterior circle are used, and liquid phase is entered
Fractionating column obtains one or more of naphtha cut, kerosene distillate, diesel oil distillate and hydrocracking tail oil.Tail oil can part
Or all loop back first paragraph or second segment reaction zone, or directly go out device.
In the inventive method, the raw oil obtained using deep vacuum distillation technology is done and is significantly improved so that nitrogen content, sulfur contain
Amount, asphalitine, carbon residue and trace metal impurities content substantially increase.Except because viscosity increase causes raw oil into catalyst
Portion diffusion speed slow down, so as to reduce outside response speed, the non-hydrocarbon compound for also bringing more, structure increasingly complex with
And the impurity such as polycyclic aromatic hydrocarbon, colloid, asphalitine, heavy metal, substantially increase hydrogenation difficulty.
In the inventive method, first paragraph reaction zone and second segment reaction zone using Hydrobon catalyst can be ability
The arbitrary product in domain.Hydrocracking catalyst can select suitable product according to the Spreading requirements of product, be such as fecund
Intermediate oil（Kerosene and diesel oil）Oil type hydrocracking catalyst in then selecting, selects light oil type to add if for voluminous Petroleum
Hydrogen Cracking catalyst, selects mobile type hydrocracking catalyst if for flexibly production Petroleum and intermediate oil.Above-mentioned choosing
It is content well-known to those skilled in the art to select.Hydrobon catalyst and hydrocracking catalyst under reactive state, plus
Hydrogen activity component is sulphided state.
In the inventive method, mainly there is the hydrodesulfurization of raw material, denitrogenation, deoxidation, aromatic hydrocarbons saturation etc. in first paragraph reaction zone
Reaction；Proceed the reaction such as hydrodesulfurization, denitrogenation, deoxidation, aromatic hydrocarbons saturation on the Hydrobon catalyst of second segment reaction zone,
Hydrocracking reaction is carried out on three-zone hydrocracking catalyst.
Compared with prior art, hydrocracking process of the invention has advantages below：
1st, those skilled in the art know, for the height that deep drawing wax oil is representative does raw material, although its nitrogen content loses
Obtain very high, but as the structure of nitrogen-containing compound is extremely complex, the nitrogen in high boiling fraction is but difficult to by routine
Method of hydrotreating is removed.In the inventive method, first by first paragraph hydrofinishing, most nitrogen impurity is removed；Then
In second segment reaction zone, under the atmosphere of low ammonia, the wax oil to being stripped of most of the nitrogen impurity is further hydrogenated with
Refined, lower ammonia partial pressure greatly slow down ammonia for advanced nitrogen and the inhibitory action of aromatic hydrocarbons saturation such that it is able to than
Under conditions of relatively relaxing, the obstinate nitrogen impurity in the part is removed, so as to provide qualified original for being hydrocracked for downstream
Material.
2nd, in first paragraph reaction zone, in the beds on top, height is done raw oil and carries out hydrofinishing with hydrogen
Reaction, cocurrent reaction effluent are separated in gas-liquid separation zone, there is suppression to make denitrogenation by what hydrogenation process was generated in time
Ammonia is removed by separating, so as to the carrying out for being conducive to countercurrent hydrogenation to react；Cocurrent hydrogenated liquid is then urged in bottom with hydrogen
In agent bed, counter current contacting carries out hydrogenation reaction, and the ammonia that course of reaction is generated also leaves reactor through gas-liquid separation zone.The
Gas and liquid flowing and gas-liquid countercurrent flow is taken simultaneously in one section, it is further provided a kind of especially suitable advanced nitrogen and saturation virtue
The hydrogenation atmosphere of hydrocarbon.And ammonia is reduced to into minimum to the inhibitory action of Hydrobon catalyst, give full play to hydrofinishing catalysis
The activity of agent such that it is able to carry out advanced nitrogen under conditions of mitigation.
3rd, the present invention does height according to raw oil, and nitrogen-containing compound is difficult to the characteristics of removing, preferably in first paragraph reaction zone
It is middle to prepare the Hydrobon catalyst that carrier is produced using by chloride process, it is characterized in that duct is big and concentrates, impurity content
Low, the effect of carrier and metal is strong, can more effectively reduce inhibitory action of the ammonia to catalyst, especially to processing high level cadre inferior
Point raw material has more preferable activity stability；And select to prepare carrier life using by sulphate method in second segment reactor
The Hydrobon catalyst of product, is characterized in that duct is relatively small and disperses, and the effect of carrier and metal is relatively weak.Second
Hydrobon catalyst in section has higher active and more preferable activity for the raw material for being stripped of most of the nitrogen impurity
Stability.So as to the level of both catalyst can preferably play the activity of hydrogenation catalyst with system, realize advanced nitrogen
While extension fixture service cycle.
4th, the hydrocracking tail oil that the 3rd section of reaction zone obtains can also partly loop back the hydrogenation of first paragraph or second segment
Finishing reactor, on the one hand can reduce the viscosity that height does raw material, greatly improve raw oil diffusion velocity on a catalyst,
Improve reaction efficiency；On the other hand deep hydrofinishing can be carried out to unsaturated aromatic hydrocarbons further.
5th, as hydrofining reaction temperature is substantially reduced, such that it is able to improve the service cycle of device, process more bad
The raw material of matter or under same service cycle improve device working ability.
Description of the drawings
Fig. 1 is a kind of principle process chart of the present invention.
Specific embodiment
Height used by the present invention is done the deasphalted oil that raw oil can be crude oil, shale oil, coal artificial oil and crude oil and is subtracted
One or more in the fractions such as pressure deep drawing distillate.
Hydrobon catalyst used in first paragraph reaction zone and second segment reaction zone can be that conventional heavy evaporates
Divide oily Hydrobon catalyst.Conventional hydro catalyst for refining generally comprises carrier and the hydrogenation metal component being loaded on carrier,
Generally include group VIB active metal component such as tungsten and/or molybdenum in the periodic table of elements, in terms of metal oxide weight 8% ~ 35%,
It is preferred that 12% ~ 30%；And the VIIIth race's active metal component such as nickel and/or cobalt, in terms of metal oxide weight 1% ~ 7%, preferably
1.5%~6%.The carrier that Hydrobon catalyst is used be inorganic refractory oxide, such as can selected from aluminium oxide, amorphous silicon aluminium,
One or more in silicon oxide and titanium oxide.Suitable adjuvant component, the such as unit such as phosphorus, boron can also be included in catalyst
Element.
In the inventive method, the catalyst that special recommendation is had the following properties that used in first paragraph reaction zone：Catalyst
Average pore diameter be 7.5 ~ 9.5nm, preferably 8 ~ 9nm；The pore volume in the hole of 4 ~ 10nm of bore dia accounts for the volume fraction of total pore volume
70% ~ 90%, preferably 75% ~ 85%；<The pore volume in 4nm holes accounts for less than the 5% of total pore volume.The hydrofinishing that first paragraph reaction zone uses
Catalyst, is usually prepared the catalyst of carrier production by chloride process, and the sintering temperature of catalyst is typically left at 480 DEG C
It is right.Catalyst used in first paragraph reaction zone can select existing business Hydrobon catalyst, or according to this area
Method prepare satisfactory catalyst.
As the nitrogen content of raw oil is removed to relatively low level, second segment reaction zone by first paragraph reaction zone
The Hydrobon catalyst that can be used using first paragraph reaction zone.The present invention is preferably in second segment reaction zone using with following
The catalyst of property：The average pore diameter of catalyst is 4 to less than 7.5nm, preferably 5 ~ 7nm；Its median pore diameter is 4 ~ 10nm's
It is 50 ~ 75%, preferably 55 ~ 65% that the pore volume in hole accounts for the volume fraction of total pore volume；<The pore volume in the hole of 4nm accounts for the volume integral of total pore volume
Number generally below 10%.Wherein compared with the Hydrobon catalyst in first paragraph, second segment Hydrobon catalyst it is average
Bore dia wants little 0.5 ~ 3nm, preferably little 1.0 ~ 2.5nm；The volume fraction that the hole of 4 ~ 10nm of aperture accounts for total pore volume is little 10 ~ 30 hundred
Fraction, preferably little 15 ~ 25 percent.Catalyst in second segment reaction zone is usually by sulphate such as aluminum sulfate method
The catalyst of carrier production is prepared, the sintering temperature of catalyst is typically at 450 DEG C or so.Catalysis used in second segment reaction zone
Agent can select existing business Hydrobon catalyst, or prepare satisfactory catalyst according to the method for this area.
Or can be with the body phase hydrogenation catalyst used in second segment reaction zone, further to improve second in the present invention
The hydrogenation temperature of section reaction zone.Body phase hydrogenation catalyst contains tri- kinds of metal components of Mo, W, Ni, in oxidized catalyst W, Ni with
Composite oxides form is present：NixWyOz, z=x+3y, Mo are present with oxide form：MoO3；Composite oxides NixWyOzMiddle x
Ratio with y is 1:8~8:1, composite oxides NixWyOzWith oxide M oO3Weight ratio be 1:10~10:1；Bulk phase catalyst
Middle composite oxides NixWyOzWith oxide M oO3Gross weight content be 40% ~ 100%.Can be as needed in bulk phase catalyst
Containing the one kind in the components such as aluminium oxide, silicon oxide, amorphous silica-alumina, phosphorous oxides, titanium oxide, Zirconium oxide, molecular sieve
Or it is several, these components weight content in the catalyst is 0 ~ 60%, preferably 20% ~ 50%.The specific surface area of bulk phase catalyst
For 120 ~ 400m2/ g, pore volume are 0.10 ~ 0.50mL/g.Body phase hydrogenation catalyst can select Fushun Petrochemical Research Institute to open
The commercial catalysts sent out, or be prepared according to the Conventional wisdom of this area.
3rd section of hydrocracking reaction area can use routine business hydrocracking catalyst, due to can by charging
Impurity content takes off relatively low, need not using resistance to nitrogen hydrocracking catalyst, it is possible to use business hydrocracking catalyst remove
Can be from the business Catalyst For Single-stage Hydrocracking with resistance to organic nitrogen function, such as Fushun Petrochemical Research Institute develops
ZHC-01, ZHC-02, ZHC-04, FC-14, FC-28, the ICR126 etc. that FC-34, CHEVRON company develops.Can be with
Using such as：DHC-32, DHC-39, HC-43, HC-115 of Uop Inc. etc., what Fushun Petrochemical Research Institute developed
3971st, 3974,3976, FC-12, FC-16, FC-26 etc..
The present invention is explained further below in conjunction with drawings and Examples.
As shown in Figure 1：Height is done raw oil and enters first paragraph hydrogenation essence after pipeline 1 is mixed with the recycle hydrogen of pipeline 2
The cocurrent reaction zone A areas of reactor processed 3 carry out the impurity such as hydrofining reaction, removing part S, N, O, and A areas effluent enters gas
Liquid Disengagement zone C areas are separated, and gas phase reaction effluent Jing pipelines 4 draw reactor, and C areas are obtained liquid phase and managed with B areas bottom Jing
The new hydrogen that line 5 is introduced carries out hydrofining reaction in B areas counter current contacting；After countercurrent hydrogenation, gas enters gas-liquid separation zone C areas simultaneously
Discharge, the liquid that first paragraph hydrofining reactor is obtained mixed with the recycle hydrogen of pipeline 7 through pipeline 6, into second segment plus
Hydrogen finishing reactor 8 proceeds the supplementary hydrogen of deep hydrofinishing reaction, second segment reaction effluent Jing pipelines 9 and pipeline 10
Hydrocracking reaction is carried out into hydrocracking reactor 11 after mixing, hydrocracking reaction effluent Jing pipelines 12 are entered and separated
Device 13 is separated, after isolating gas 14, liquid through line 15 enter fractionating column 16, isolate gas 17, Petroleum 18, coal
Oil 19, diesel oil 20 and tail oil 21, separator 13 generally include high-pressure separator and low pressure separator.A part for tail oil 21 can be with
Return the entrance of first paragraph hydrofining reactor 3 or second segment hydrofining reactor 8.
The present invention program and effect are illustrated below by embodiment.Hydrocracking catalyst used is Fushun petrochemical industry
The commercial catalyst of academy's development and production, the property of raw materials used oil are listed in table 1.The property of used Hydrobon catalyst
It is listed in table 2.In the present invention, wt% is weight percentage or weight content.
Embodiment 1
Using the technological process shown in Fig. 1, three-zone hydrocracking passes through flow process using one way.Filling catalysis in first paragraph
Agent A, second segment loading catalyst A.First paragraph finishing reactor top adopts gas and liquid flowing flow process, bottom to adopt gas-liquid counter current stream
Journey, cocurrent section are 1 with the Catalyst packing volume ratio of adverse current section:1.
Embodiment 2
First paragraph and the equal loading catalyst B of second segment, other are with embodiment 1.
Embodiment 3
First paragraph loading catalyst A, second segment loading catalyst B.Other are with embodiment 1.
Comparative example 1
Using conventional two-stage reforming technique.Hydrofining reaction area only uses Hydrobon catalyst A, hydrogenation to split
Change section and use FC-50 catalyst.Hydrocracking reaction section is controlled wherein>370 DEG C of conversion ratios are about 70wt%.
Comparative example 2
Using conventional two-stage reforming technique.Hydrofining reaction area only uses Hydrobon catalyst B, hydrogenation to split
Change section and use FC-50 catalyst.Hydrocracking reaction section is controlled wherein>370 DEG C of conversion ratios are about 70wt%.
Comparative example 3
Technique basic procedure is with embodiment 1.Only with cocurrent technological process in first paragraph reaction zone, first paragraph reaction zone stream
Go out thing to be separated, liquid carries out deep hydrofinishing reaction, second segment hydrogenation reaction stream with hydrogen into second segment reaction zone
Going out thing carries out hydrocracking reaction with hydrogen make-up into the 3rd section of reaction zone.
Wherein first paragraph reaction zone uses Hydrobon catalyst A, second segment reaction zone to use Hydrobon catalyst B,
3rd section uses FC-50 catalyst.Hydrocracking reaction section is controlled wherein>370 DEG C of conversion ratios are about 70wt%.
The result of the test that embodiment 1-3 operates 500 and 6000 hours is listed in table 3.The examination that comparative example 1-3 operates 500 hours
Test result and be listed in table 4.
1 raw oil of table.
| Raw oil | Deep drawing wax oil |
| Density/kg m-3 | 929.3 |
| Boiling range/DEG C | 367~600 |
| Sulfur content/wt% | 2.99 |
| Nitrogen content/mg g-1 | 1073 |
| Condensation point/DEG C | 28 |
| BMCI values | 50.7 |
2 Hydrobon catalyst of table.
| Numbering | A | B |
| Carrier | Aluminium oxide | Aluminium oxide |
| MoO3, wt% | 24.9 | 24.5 |
| NiO, wt% | 4.12 | 4.26 |
| P, wt% | 2.67 | 2.71 |
| Average pore diameter, nm | 8.4 | 6.5 |
| 4 ~ 10nm holes account for the ratio of total pore volume, v% | 85 | 61 |
3 result of the test of table.
| Embodiment | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Process conditions | |||
| Catalyst | (A/A)/A/FC-50* | (B/B)/B/FC-50* | (A/A)/B/FC-50* |
| Reaction pressure/MPa | 15.7 | 15.7 | 15.7 |
| Volume space velocity/h-1 | (2.4/2.4)/1.2/1.8 | (2.4/2.4)/1.2/1.8 | (2.4/2.4)/1.2/1.8 |
| Hydrogen to oil volume ratio | 900/(900/900)/1300 | 900/(900/900)/1300 | 900/900/1300 |
| First paragraph denitrification percent, wt% | 86 | 86 | 86 |
| Cracking zone>370 DEG C of conversion per pass, wt% | 70.7 | 70.9 | 71.1 |
| Operating 500 hours | |||
| Reaction temperature/DEG C | (368/368)/374/382 | (365/365)/371/382 | (368/368)/371/382 |
| Major product property | |||
| Jet fuel | |||
| Yield, wt% | 16.69 | 16.71 | 17.02 |
| Smoke point, mm | 28 | 27 | 28 |
| Diesel oil | |||
| Yield, wt% | 6.88 | 6.91 | 7.11 |
| Cetane number | 68.3 | 67.1 | 68.5 |
| Tail oil | |||
| Yield | 29.3 | 29.1 | 28.9 |
| BMCI values | 10.4 | 10.3 | 10.2 |
| Viscosity index (VI) | 138 | 137 | 138 |
| Operating 6000 hours | |||
| Reaction temperature/DEG C | (374/374)/377/385 | (377/377)/378/385 | (374/374)/378/385 |
| Major product property | |||
| Jet fuel | |||
| Yield, wt% | 17.45 | 17.76 | 17.43 |
| Smoke point, mm | 27 | 26 | 27 |
| Diesel oil | |||
| Yield, wt% | 6.63 | 6.81 | 6.72 |
| Cetane number | 67.7 | 66.8 | 67.5 |
| Tail oil | |||
| Yield | 29.2 | 29.2 | 29.2 |
| BMCI values | 10.7 | 10.6 | 10.7 |
| Viscosity index (VI) | 137 | 136 | 137 |
4 result of the test of table.
| Numbering | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Catalyst | A/FC-50* | B/FC-50* | A/B/FC-50# |
| Reaction pressure/MPa | 15.7 | 15.7 | 15.7 |
| Hydrogen to oil volume ratio | 900/1300 | 900/1300 | 900/900/1300 |
| Volume space velocity/h-1 | 0.6/1.8 | 0.6/1.8 | 1.2/1.2/1.8 |
| Reaction temperature/DEG C | 395/382 | 388/382 | 377/371/382 |
| First paragraph denitrification percent, wt% | — | — | 86 |
| Cracking zone>370 DEG C of conversion per pass, wt% | ~70 | ~70 | ~70 |
| Major product property | |||
| Jet fuel | |||
| Yield, wt% | 17. 87 | 17.71 | 17.83 |
| Smoke point, mm | 24.0 | 24.0 | 28.0 |
| Diesel oil | |||
| Yield, wt% | 7.57 | 7.68 | 7.62 |
| Cetane number | 62.4 | 62.9 | 62.7 |
| Tail oil | |||
| Yield | 30.0 | 30.0 | 30.0 |
| BMCI values | 12.1 | 11.9 | 11.0 |
| Viscosity index (VI) | 129 | 128 | 137 |
Embodiment by more than shows that the inventive method can give full play to hydrogenation essence when processing height does raw material
The activity of catalyst processed and hydrocracking catalyst.
As hydrofinishing and hydrocracking reaction temperature are substantially reduced, such that it is able to improve the service cycle of device, or
Person improves the working ability of device under same service cycle.
Claims (12)
1. a kind of height does raw material hydrocracking process, including herein below：
（1）Under Hydrofinishing conditions, height does raw oil and hydrogen is mixed into first paragraph reaction zone, and first paragraph reaction zone makes
With Hydrobon catalyst, the top of first paragraph reaction zone is gas and liquid flowing reaction zone, and cocurrent reaction effluent is into gas-liquid point
Separated from area, gas draws reactor；Liquid enters the beds of bottom, and the hydrogen introduced with reactor bottom is entered
Row counter current contacting is reacted, and reacted gas leaves reactor from gas-liquid separation zone；The denitrification percent of first paragraph reaction zone is controlled to
60wt%~95wt%；It is more than 550 DEG C that described height does the end point of distillation of raw material；
（2）The generation oil that first paragraph reaction zone obtains enters second segment reaction zone after mixing with hydrogen, carries out Deep Hydrotreating
Reaction, second segment reaction zone uses Hydrobon catalyst；
（3）The reaction effluent that second segment reaction zone obtains enters the 3rd section of reaction zone, the 3rd section of reaction together with hydrogen make-up
Hydrocracking catalyst is used in area；
（4）The reaction effluent that 3rd section of reaction zone obtains enters separator, obtains gas and liquid, and liquid is obtained after being fractionated into
Various hydrocracked products；
Wherein, the Hydrobon catalyst used in first paragraph has the following properties that：The average pore diameter of catalyst be 7.5 ~
9.5nm, it is 70 ~ 90% that aperture is the volume fraction that the hole of 4 ~ 10nm accounts for total pore volume；Second segment reaction zone using hydrofinishing urge
Agent has the following properties that：For 4 to less than 7.5nm, aperture accounts for always the average pore diameter of catalyst for the pore volume in the hole of 4 ~ 10nm
The volume fraction of pore volume is 50 ~ 75%；Compared with the Hydrobon catalyst in first paragraph, hydrofinishing catalysis in second segment
The average pore diameter of agent wants little 0.5 ~ 3nm, and the volume fraction that the hole of 4 ~ 10nm of aperture accounts for total pore volume is little 10 ~ 30 percentage points.
2. according to the technique described in claim 1, it is characterised in that it is more than 570 DEG C that described height does the end point of distillation of raw material.
3. according to the technique described in claim 2, it is characterised in that it is 580～620 that described height does the end point of distillation of raw material
℃。
4. according to the arbitrary described technique of claim 1-3, it is characterised in that described height is done the nitrogen content of raw material and existed
500mg·g-1More than.
5. according to the technique described in claim 1, it is characterised in that the hydrofinishing described in first paragraph and second segment reaction zone
Catalyst includes carrier and the hydrogenation metal component being loaded on carrier, and catalyst includes group VIB metal group in the periodic table of elements
Divide in terms of metal oxide weight 8% ~ 35%, and metal component of group VIII in terms of metal oxide weight 1% ~ 7%.
6. according to the technique described in claim 1, it is characterised in that compared with the Hydrobon catalyst in first paragraph, the
The volume fraction that the hole of the little 1.0 ~ 2.5nm of average pore diameter of secondary hydrogenation catalyst for refining, 4 ~ 10nm of aperture accounts for total pore volume is little
15 ~ 25 percentage points.
7. according to the technique described in claim 1, it is characterised in that the Hydrobon catalyst used in first paragraph reaction zone
Average pore diameter is 8 ~ 9nm, and it is 75% ~ 85% that the pore volume in the hole of 4 ~ 10nm of bore dia accounts for the volume fraction of total pore volume.
8. according to the technique described in claim 6 or 7, it is characterised in that the Hydrobon catalyst that second segment reaction zone uses
Average pore diameter be 5 ~ 7nm, its median pore diameter for 4 ~ 10nm hole pore volume account for total pore volume volume fraction be 55% ~ 65%.
9. according to the technique described in claim 1, it is characterised in that the process conditions of cocurrent reaction zone in first paragraph reaction zone
For：Average reaction temperature is 250 ~ 500 DEG C, and reaction pressure is 5.0 ~ 20.0MPa, and hydrogen to oil volume ratio is 100:1~4000:1, liquid
When volume space velocity be 1.0 ~ 10.0h-1；In first paragraph reaction zone, the process conditions of counter-flow reaction zone are：Average reaction temperature is 250
~ 500 DEG C, reaction pressure is 5.0 ~ 20.0MPa, and hydrogen to oil volume ratio is 100:1~2000:1, during liquid volume space velocity be 1.0 ~
10.0h-1。
10. according to the technique described in claim 1, it is characterised in that the process conditions of second segment reaction zone are：Average response temperature
Spend for 330 ~ 480 DEG C, reaction pressure is 5.0 ~ 20.0MPa, and hydrogen to oil volume ratio is 100:1~4000:1, during liquid, volume space velocity is
0.2~4.0h-1。
11. according to the technique described in claim 1, it is characterised in that the process conditions that the 3rd section of reaction zone is hydrocracked are：It is flat
Reaction temperature is 250 ~ 500 DEG C, and reaction pressure is 5.0 ~ 20.0MPa, and hydrogen to oil volume ratio is 100:1~4000:1, volume during liquid
Air speed is 1.0 ~ 10.0h-1。
12. according to the technique described in claim 1, it is characterised in that body phase hydrogenation catalyst, body used in second segment reaction zone
Phase hydrogenation catalyst contains tri- kinds of metal components of Mo, W, Ni, and in oxidized catalyst, W, Ni are present with composite oxides form：
NixWyOz, z=x+3y, Mo are present with oxide form：MoO3；Composite oxides NixWyOzThe ratio of middle x and y is 1:8~8:1,
Composite oxides NixWyOzWith oxide M oO3Weight ratio be 1:10~10:1；Composite oxides Ni in bulk phase catalystxWyOz
With oxide M oO3Gross weight content be 40% ~ 100%.
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|---|---|---|---|---|
| US5183556A (en) * | 1991-03-13 | 1993-02-02 | Abb Lummus Crest Inc. | Production of diesel fuel by hydrogenation of a diesel feed |
| CN1552812A (en) * | 2003-05-31 | 2004-12-08 | 中国石油化工股份有限公司 | Deep desulphurizing and dearomating process for diesel oil |
| CN103102957A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Two-stage hydrocracking method for high-nitrogen raw material |
| CN103102966A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | High nitrogen raw material hydrocracking method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5183556A (en) * | 1991-03-13 | 1993-02-02 | Abb Lummus Crest Inc. | Production of diesel fuel by hydrogenation of a diesel feed |
| CN1552812A (en) * | 2003-05-31 | 2004-12-08 | 中国石油化工股份有限公司 | Deep desulphurizing and dearomating process for diesel oil |
| CN103102957A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Two-stage hydrocracking method for high-nitrogen raw material |
| CN103102966A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | High nitrogen raw material hydrocracking method |
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