CN104611009B - Poor-quality heavy distillate oil hydrotreating method - Google Patents
Poor-quality heavy distillate oil hydrotreating method Download PDFInfo
- Publication number
- CN104611009B CN104611009B CN201310540359.3A CN201310540359A CN104611009B CN 104611009 B CN104611009 B CN 104611009B CN 201310540359 A CN201310540359 A CN 201310540359A CN 104611009 B CN104611009 B CN 104611009B
- Authority
- CN
- China
- Prior art keywords
- reaction zone
- catalyst
- segment
- paragraph
- accordance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a poor-quality heavy distillate oil hydrotreating method. According to the method, under a hydrorefining condition, a heavy distillate oil raw material and hydrogen gas are mixed and enter a first-stage reaction zone to carry out a hydrotreating reaction, the first-stage reaction zone effluent is subjected to gas-liquid separation to obtain a liquid phase, the liquid phase enters a second-stage reaction zone to carry out a hydrotreating reaction, and the second-stage reaction zone reaction effluent is separated to obtain the hydrotreating reaction product. Compared with the existing hydrotreating technology in the prior art, the method of the present invention has the following advantages that: the product quality and the processing capability of the device can be substantially improved, or the operating pressure can be reduced and the operating cost can be reduced under the same product quality and processing capability condition.
Description
Technical field
The invention discloses a kind of hydrotreating method, a kind of two-stage hydrogenation processing method processing inferior heavy distillate feedstock.
Background technology
Along with the high speed development of Chinese national economy, PETROLEUM PROCESSING ability quickly increases.Meanwhile, crude oil price remains high so that the proportion that crude oil procurement cost accounts in oil refining totle drilling cost is substantially increased, and the profit margin of oil refining enterprise is greatly reduced.Additionally, owing to crude quality is deteriorated year by year, being significantly increased of import high-sulfur height nitrogen crude runs, environmental protection is the strictest to the requirement of oil refining process and petroleum product-quality, and clear gusoline and industrial chemicals demand are continuously increased by market so that the progress of hydrogen addition technology level is had higher requirement by market.
In catalytic cracking process, the raw material of high sulfur content will cause the sulfur content of product petrol and diesel oil can not reach cleaning product requirement, but also can make the SO in catalytic cracking flue gasXDischarge exceeds standard, and the high nitrogen-containing in catalytically cracked material will increase the consumption of catalyst, increases operating cost.Hydrotreating of FCC feedstock technology can be greatly lowered sulfur nitrogen metal impurities content, improves product property, improves purpose product yield, has therefore obtained increasingly being widely applied.
Existing hydrotreating of FCC feedstock technique, as US4780193 discloses a kind of hydrorefining catalyst cracked charge method, produces the gasoline blend component that octane number is higher.CN101007964 discloses a kind of method of hydrotreating producing fine quality catalytic cracking raw material; but its operation pressure is low; be not suitable for processing high-nitrogen stock; CN101987967 discloses the hydrotreating method of a kind of deep vacuum distillation wax oil; use two sections of flow processs; but its first paragraph uses the most weak hydrogenation protecting agent of activity and demetalization protective agent; second segment uses hydrodesulfurization and hydrodenitrogenation catalyst; cause unit capacity the highest owing to catalyst overall activity is relatively low during processing high nitrogen-containing raw material, or it is the highest to process the degree of depth.
Along with current crude quality worse becoming, impurity content increases, and crude oil decompression is deep and the exploitation of other unconventional energy resource so that the raw material impurity content of hydrotreating is more and more higher, and the particularly nitrogen content of some hydrotreated feed is higher, and existing hydrotreating method is when processing the hydrogenating materials of high nitrogen-containing, needing higher reaction temperature, higher reaction pressure or relatively low operation air speed, the working ability of device declines, energy consumption increases simultaneously, and the operation cycle shortens.
Summary of the invention
For the deficiencies in the prior art, the two-stage hydrogenation that it is an object of the invention to provide a kind of improvement processes technique, the inferior feedstock oil that processing nitrogen content is the highest.Compare compared with hydrotreating techniques, be greatly improved product quality and the working ability of device, or under the conditions of same product quality and working ability, drop low operating pressure, reduce operating cost.
A kind of inferior heavy distillate hydrogenation processing method of the present invention, including herein below:
(1) inferior heavy distillate and hydrogen are mixed into first paragraph reaction zone, and first paragraph reaction zone includes Hydrobon catalyst, and the denitrification percent of first paragraph reaction zone controls as 20wt% ~ 70wt%；
(2) first paragraph reaction zone effluent entrance separator separates, and obtains gas phase and liquid phase, and gas phase is through imurity-removal (predominantly NH3And H2S) can recycle after；
(3) step (2) obtains entering second segment reaction zone after liquid phase mixes with hydrogen and carries out hydrotreating reaction, and second segment reaction zone uses Hydrobon catalyst；
(4) second segment reaction zone obtains effluent entrance piece-rate system, is isolated to hydrotreatment products.
In the inventive method, the nitrogen content of the inferior heavy distillate described in step (1) is generally 2500 more than μ g/g, preferably 3000 more than μ g/g, most preferably 3000～15000 μ g/g.The initial boiling point of inferior heavy distillate feedstock is generally 220～450 DEG C, preferably 300～420 DEG C；The end point of distillation is generally 470～550 DEG C, preferably 500～550 DEG C.Described inferior heavy distillate is typically used as the raw material of catalytic cracking unit.
In the hydrotreating method of the present invention, wherein first paragraph reaction zone and second segment reaction zone are the fixed bed hydrogenation reaction that gas and liquid flowing is downward.
Separator described in step (2) can be high pressure hot separator or cold high pressure separator.
According to the hydrotreating method of the present invention, the most in step (3), preferably the liquid phase after first paragraph reaction zone gas-liquid separation in step (2) is first washed with water, to reduce dissolved ammonia (NH in first paragraph hydrofinishing generation oil3) content, through washing after liquid phase again with hydrogen enter second segment reaction zone.Water washing operations described herein is the routine operation of those skilled in the art.
In the inventive method, the piece-rate system described in step (4) generally includes high-pressure separator, low pressure separator and fractionating column.
In the inventive method, the denitrification percent general control 20wt% ~ 70wt% of first paragraph reaction zone, it is preferably controlled to 30wt% ~ 60wt%.The process conditions of first paragraph reaction zone are generally: average reaction temperature is 330 ~ 480 DEG C, preferably 350 ~ 450 DEG C；Reaction pressure is 5.0MPa ~ 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 0.2 ~ 4.0h-1, preferably 0.5 ~ 3.0h-1。
In the inventive method, wherein the process conditions of second segment reaction zone are generally: 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 0.2 ~ 4.0h-1, preferably 0.5 ~ 3.0h-1。
In the inventive method, according to the scale of device, first paragraph reaction zone can arrange one or several reactors, and second segment reaction zone can also arrange one or several reactors.
In the inventive method, after first paragraph reaction zone reaction effluent carries out gas-liquid separation, gas phase can use through removing hydrogen sulfide and ammonia Posterior circle, and liquid phase enters back into second segment reaction zone, carries out Deep Hydrotreating reaction with hydrogen after washing hydrogen sulfide and ammonia off preferably through washing.
In the inventive method, first paragraph reaction zone and second segment reaction zone can be respectively provided with recycle hydrogen system or share a set of recycle hydrogen system.When first paragraph reaction zone and second segment reaction zone share a set of recycle hydrogen system, need hydrogen flow path is optimized: the gas phase of first paragraph reaction zone reaction effluent gas-liquid separation carries out depriving hydrogen sulphide and deamination, it is subsequently used for second segment reaction zone, gas phase after the reaction effluent gas-liquid separation of second segment reaction zone is cycled to used in first paragraph reaction zone, and the new hydrogen that course of reaction is supplemented enters second segment reaction zone
In the inventive method, mainly there is partial desulfurization and the part denitrification reaction of raw material in first paragraph reaction zone；The reactions such as deep hydrodesulfurizationof, denitrogenation, deoxidation, aromatic hydrocarbons are saturated are proceeded on the Hydrobon catalyst of second segment reaction zone.
Compared with prior art, the process of the present invention has an effect highlighted below:
1, when processing the highest inferior feedstock oil of nitrogen content, the present invention can hydrogen sulfide in substantially reduction system and ammonia content, improve hydrogen dividing potential drop, effectively play Hydrobon catalyst and the activity of hydrocracking catalyst.Be hydrocracked at present-isomerization dewaxing combined unit Hydrocracking unit charging generally comprise vacuum distillate, solvent refining deasphalted oil or Fischer-Tropsch synthesis oil, and inferior raw material is after the first reaction zone carries out the reactions such as desulfurization, denitrogenation, deoxidation, aromatic hydrocarbons are saturated, second reaction zone feedstock quality reaches catalytic cracking or the feedstock quality requirement being hydrocracked, and can expand high-quality catalysis or the source of hydrogenating materials.
2, those skilled in the art are it is generally believed that Hydrobon catalyst has resistance to nitrogen, and hydrogen sulfide and ammonia in recycle hydrogen do not have inhibitory action to catalyst.But by the in-depth analysis of existing hydroprocessing technique is learnt, when the raw oil that processing nitrogen content is the highest, owing to the impurity contents such as sulfur nitrogen are the highest, course of reaction generates substantial amounts of hydrogen sulfide and ammonia, and the nitrogen removal performance of Hydrobon catalyst is produced the strongest inhibitory action.If using the conventional method of this area, need the denitrification effect needed for could obtaining under higher reaction temperature.And the present invention is by optimizing hydrofining technology flow process, Hydrobon catalyst is assigned in different refining reaction districts by suitable proportion；And achieve while the identical hydrogenation removing impurities matter degree of depth in second segment finishing reactor, significantly reduce reaction temperature, improve hydrofinishing effluent quality, and extend service cycle.Meanwhile, the relatively low temperature of second segment also can promote aromatic hydrocarbons saturated reaction, and denitrification reaction is generally ring-opening reaction, so that reaction temperature reduces further.That is, when processing same inferior raw material under identical air speed, owing to two-stage reaction has higher hydrogen dividing potential drop and aromatic hydrocarbons saturated reaction faster, use two reactors to be removed to certain nitrogen content and use a reactor to need lower average reaction temperature ratio.
3, the present invention is according to the high feature of raw oil nitrogen content, preferably use in first paragraph reaction zone and prepared, by chloride process, the Hydrobon catalyst that carrier produces, it is characterized in that duct is big and concentrates, impurity content is low, the effect of carrier and metal is strong, there is more preferable resistant to ammonia performance, can more effectively reduce the ammonia inhibitory action to catalyst, especially processing inferior raw material be had more preferable activity stability；And be preferably used in second segment reactor and prepared, by sulphate method, the Hydrobon catalyst that carrier produces, it being characterized in that duct is relatively small and disperses, the effect of carrier and metal is relatively weak.Catalyst for refining in second segment has higher activity and more preferable activity stability for the raw material being stripped of most of the nitrogen impurity.Thus, the grating of both catalyst can preferably play the activity of catalyst.
4, first paragraph reaction effluent liquid phase preferably first passes through and enters back into second segment hydrofining reactor after hydrogen sulfide and ammonia are washed in washing off, more can reduce the ammonia content in second segment reactor further, more effectively play the activity of second segment Hydrobon catalyst.
Accompanying drawing explanation
Fig. 1 is a kind of principle process chart of the present invention.
Detailed description of the invention
The two-stage hydrogenation of the present invention processes technical process, and a kind of idiographic flow includes:
(1) inferior heavy distillate feedstock oil and hydrogen are mixed into the reactions such as first paragraph hydrotreating reactor generation hydrodesulfurization, denitrogenation, deoxidation, aromatic hydrocarbons are saturated；(2) first paragraph hydrotreating generates oil and enters high-pressure separator, is continuing with after the gas removal ammonia separated, hydrogen sulfide, and the liquid separated enters second segment hydrotreating reactor；(3) first paragraph hydrotreating generates oil and enters second segment hydrotreating reactor with hydrogen mixing, the reaction such as proceed to occur hydrodesulfurization, denitrogenation, deoxidation, aromatic hydrocarbons saturated；(4) second segment hydrogenation reaction effluent enters separator, and the gas separated recycles, and the liquid separated enters fractionating system；Can isolate one or more in Petroleum, diesel oil and tail oil as required, tail oil can feed as catalytic cracking unit, or feeds directly as catalytic cracking unit without isolation.
Inferior heavy distillate used by the present invention can be one or more in the fraction such as the wax tailings of crude oil, deasphalted oil, shale oil and coal artificial oil, crude oil deep vacuum distillation distillate.The end point of distillation (engler's fractional distillation) of described inferior heavy distillate generally 470 ~ 550 DEG C.
Hydrobon catalyst used in first paragraph reaction zone and second segment reaction zone can be conventional heavy distillate Hydrobon catalyst.Conventional hydro catalyst for refining generally comprises carrier and the hydrogenation metal component being loaded on carrier, generally includes group VIB active metal component such as tungsten and/or molybdenum in the periodic table of elements, and in terms of oxide weight 8% ~ 35%, preferably 12% ~ 30%；And the VIIIth race's active metal component such as nickel and/or cobalt, in terms of oxide weight 1% ~ 7%, preferably 1.5% ~ 6%.The carrier that Hydrobon catalyst uses is inorganic refractory oxide, such as aluminium oxide, amorphous silicon aluminium, silicon oxide, titanium oxide etc..
In the inventive method, special recommendation uses the catalyst having the following properties that in first paragraph reaction zone: the average pore diameter of catalyst is 7.5 ~ 9.5nm, preferably 8 ~ 9nm；It is 70% ~ 90% that the pore volume in the hole of bore dia 4 ~ 10nm accounts for the volume fraction of total pore volume, preferably 75% ~ 85%；< pore volume in 4nm hole accounts for less than the 5% of total pore volume.
The Hydrobon catalyst that first paragraph reaction zone uses, is usually prepared, by chloride process, the catalyst that carrier produces, and the sintering temperature in catalyst preparation process is typically at about 480 DEG C.The catalyst used in first paragraph reaction zone can select existing business Hydrobon catalyst, or prepares satisfactory catalyst according to the method for this area.
Owing to the nitrogen content of raw oil is removed to relatively low level by first paragraph reaction zone, second segment reaction zone can use the Hydrobon catalyst that first paragraph reaction zone uses, the present invention preferably uses the catalyst that has the following properties that in second segment reaction zone: the average pore diameter of catalyst is 4 to less than 7.5nm, preferably 5 ~ 7nm；Its median pore diameter is that to account for the volume fraction of total pore volume be 50% ~ 75% for the pore volume in the hole of 4 ~ 10nm, preferably 55% ~ 65%；< pore volume in the hole of 4nm accounts for the volume fraction of total pore volume and is generally below 10%.Wherein compared with the Hydrobon catalyst in first paragraph, the average pore diameter of second segment Hydrobon catalyst wants little 0.5 ~ 3nm, the least 1.0 ~ 2.5nm；The hole of aperture 4 ~ 10nm accounts for little 10 ~ 30 percents of volume fraction of total pore volume, the least 15 ~ 25 percents.
Catalyst in second segment reaction zone is usually prepared, by sulphate such as aluminum sulfate method, the catalyst that carrier produces, and the sintering temperature of catalyst preparation process is typically at about 450 DEG C.The catalyst used in second segment reaction zone can select existing business Hydrobon catalyst, or prepares satisfactory catalyst according to the method for this area.
Or the present invention can also use body phase hydrogenation catalyst, to improve the hydrogenation temperature of second segment reaction zone further in second segment reaction zone.Body phase hydrogenation catalyst contains tri-kinds of metal components of Mo, W, Ni, and in oxidized catalyst, W, Ni exist with composite oxides form: NixWyOz, z=x+3y, Mo are with oxide form existence: 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 catalystxWyOzWith oxide M oO3Gross weight content be 40% ~ 100%.Bulk phase catalyst can contain one or more in the components such as aluminium oxide, silicon oxide, amorphous silica-alumina, phosphorous oxides, titanium oxide, Zirconium oxide, molecular sieve as required, these components weight content in the catalyst is 0 ~ 60%, preferably 20% ~ 50%.The specific surface area of bulk phase catalyst is 120 ~ 400m2/ g, pore volume is 0.10 ~ 0.50mL/g.Body phase hydrogenation catalyst can select the commercial catalysts that Fushun Petrochemical Research Institute develops, or is prepared according to the Conventional wisdom of this area.
The present invention is explained further below in conjunction with drawings and Examples.
Inferior feedstock oil enters first paragraph hydrofining reactor 3 after the recycle hydrogen of pipeline 1 with pipeline 2 mixes, and carries out hydrofining reaction；First paragraph reaction effluent enters separator 5 along pipeline 4 and separates, and isolated gas goes out device through pipeline 6, can use through imurity-removal Posterior circle；The liquid phase that separator 5 obtains, after washing (not shown), through pipeline 7 with after the hydrogen of pipeline 8 mixes, enter second segment hydrofining reactor 9, remove the impurity such as sulfur, nitrogen further, second segment reaction zone effluent enters piece-rate system 11 along pipeline 10 and separates, and is separated into gas 12, Petroleum 13, diesel oil 14 and tail oil 15.Piece-rate system 11 generally includes high-pressure separator, low pressure separator and fractionating column.
Below by embodiment, the present invention program and effect are described.Raw oil character is listed in table 1, catalyst property is listed in table 2.In the present invention, wt% is weight percentage or weight content.
Table 1 raw oil.
Table 2 Hydrobon catalyst.
Embodiment 1
Use technological process shown in Fig. 1.First paragraph and second segment all use Hydrobon catalyst B.
Embodiment 2
Use technological process shown in Fig. 1.First paragraph and second segment all use Hydrobon catalyst A.
Embodiment 3
Using technological process shown in Fig. 1, first paragraph uses Hydrobon catalyst A, and second segment uses Hydrobon catalyst B.
Comparative example 1
Use prior art, only use a conversion zone to process faulty wax oil raw material, wherein use Hydrobon catalyst A.
Comparative example 2
Use prior art, only use a conversion zone to process faulty wax oil raw material, wherein use Hydrobon catalyst B.
Table 3 result of the test.
Above example shows, using two-stage hydrogenation to process technique, Hydrobon catalyst is divided into two sections of fillings, when the inferior heavy distillate feedstock that processing nitrogen content is higher, can effectively play the activity of Hydrobon catalyst, and high-quality charging can be provided for downstream catalytic cracking unit.
Owing to hydrofining reaction temperature is substantially reduced, such that it is able to improve the service cycle of device, or under same service cycle, improve the working ability of device, or drop low operating pressure when maintaining like denitrification percent.
Claims (14)
1. an inferior heavy distillate hydrogenation processing method, including herein below:
(1) inferior heavy distillate and hydrogen are mixed into first paragraph reaction zone, and first paragraph reaction zone includes Hydrobon catalyst, and the denitrification percent of first paragraph reaction zone controls as 20wt% ~ 70wt%；The nitrogen content of described inferior heavy distillate is 2500 more than μ g/g；
(2) first paragraph reaction zone effluent entrance separator separates, and obtains gas phase and liquid phase；
(3) step (2) obtains entering second segment reaction zone after liquid phase mixes with hydrogen and carries out hydrotreating reaction, and second segment reaction zone uses Hydrobon catalyst；
(4) second segment reaction zone obtains effluent entrance piece-rate system, is isolated to hydrotreatment products；
Catalyst described in first paragraph reaction zone has the property that the average pore diameter of catalyst is 7.5 ~ 9.5nm, and it is 70% ~ 90% that the pore volume in the hole of bore dia 4 ~ 10nm accounts for the volume fraction of total pore volume, and < pore volume in 4nm hole accounts for less than the 5% of total pore volume；The catalyst used in second segment reaction zone has the following properties that, the average pore diameter of catalyst is 4 to less than 7.5nm, its median pore diameter is that to account for the volume fraction of total pore volume be 50% ~ 75% for the pore volume in the hole of 4 ~ 10nm, and < pore volume in the hole of 4nm accounts for the volume fraction of total pore volume less than 10%；Wherein compared with the Hydrobon catalyst in first paragraph, the average pore diameter of second segment Hydrobon catalyst wants little 0.5 ~ 3nm, and the volume fraction that the hole of aperture 4 ~ 10nm accounts for total pore volume is little 10 ~ 30 percentage points.
The most in accordance with the method for claim 1, it is characterised in that the nitrogen content of described inferior heavy distillate is 3000 more than μ g/g.
The most in accordance with the method for claim 2, it is characterised in that the nitrogen content of described inferior heavy distillate is 3000 ~ 15000 μ g/g.
4. according to the arbitrary described method of claims 1 to 3, it is characterised in that the end point of distillation of described inferior heavy distillate is 470～550 DEG C.
The most in accordance with the method for claim 1, it is characterised in that the denitrification percent of first paragraph reaction zone controls as 30wt%～60wt%.
The most in accordance with the method for claim 1, it is characterized in that, the process conditions of first paragraph reaction zone are: average reaction temperature is 300～480 DEG C, and reaction pressure is 5.0～20.0MPa, hydrogen to oil volume ratio is 100:1～4000:1, and during liquid, volume space velocity is 0.2～4.0h-1。
The most in accordance with the method for claim 1, it is characterized in that, the process conditions of second segment reaction zone are: average reaction temperature is 250～500 DEG C, and reaction pressure is 5.0～20.0MPa, hydrogen to oil volume ratio is 100:1～4000:1, and during liquid, volume space velocity is 1.0～10.0h-1。
The most in accordance with the method for claim 1, it is characterized in that, first paragraph reaction zone and second segment reaction zone use a set of recycle hydrogen system, the gas phase of first paragraph reaction zone reaction effluent gas-liquid separation carries out depriving hydrogen sulphide and deamination, it is subsequently used for second segment reaction zone, gas phase after the reaction effluent gas-liquid separation of second segment reaction zone is cycled to used in first paragraph reaction zone, and the new hydrogen that course of reaction is supplemented enters second segment reaction zone.
The most in accordance with the method for claim 1, it is characterized in that, the Hydrobon catalyst used in first paragraph reaction zone and second segment reaction zone includes carrier and the hydrogenation metal component being loaded on carrier, catalyst includes group VIB active metal component in terms of oxide weight 8% ~ 35% in the periodic table of elements, VIIIth race's active metal component in terms of oxide weight 1% ~ 7%, carrier is inorganic refractory oxide.
The most in accordance with the method for claim 1, it is characterised in that the average pore diameter of the catalyst used in first paragraph reaction zone is 8 ~ 9nm, and it is 75% ~ 85% that the pore volume in the hole of bore dia 4 ~ 10nm accounts for the volume fraction of total pore volume.
11. in accordance with the method for claim 1, it is characterised in that the average pore diameter of catalyst used in second segment reaction zone is 5 ~ 7nm, and its median pore diameter is that to account for the volume fraction of total pore volume be 55% ~ 65% for the pore volume in the hole of 4 ~ 10nm.
12. in accordance with the method for claim 1, it is characterized in that, compared with the Hydrobon catalyst in first paragraph reaction zone, the little 1.0 ~ 2.5nm of average pore diameter of second segment Hydrobon catalyst, the volume fraction that the hole of aperture 4 ~ 10nm accounts for total pore volume is little 15 ~ 25 percentage points.
13. in accordance with the method for claim 1, it is characterized in that, using body phase hydrogenation catalyst in second segment reaction zone, described body phase hydrogenation catalyst contains tri-kinds of metal components of Mo, W, Ni, and in oxidized catalyst, W, Ni exist with composite oxides form: NixWyOz, z=x+3y, Mo are with oxide form existence: 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 catalystxWyOzWith oxide M oO3Gross weight content be 40% ~ 100%.
14. in accordance with the method for claim 13, it is characterized in that, possibly together with one or more in aluminium oxide, silicon oxide, amorphous silica-alumina, phosphorous oxides, titanium oxide, Zirconium oxide and molecular sieve in described bulk phase catalyst, these components weight content in the catalyst is 1 ~ 60 %.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310540359.3A CN104611009B (en) | 2013-11-05 | 2013-11-05 | Poor-quality heavy distillate oil hydrotreating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310540359.3A CN104611009B (en) | 2013-11-05 | 2013-11-05 | Poor-quality heavy distillate oil hydrotreating method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104611009A CN104611009A (en) | 2015-05-13 |
| CN104611009B true CN104611009B (en) | 2017-01-11 |
Family
ID=53145663
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310540359.3A Active CN104611009B (en) | 2013-11-05 | 2013-11-05 | Poor-quality heavy distillate oil hydrotreating method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104611009B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106957681A (en) * | 2017-03-31 | 2017-07-18 | 北京中科诚毅科技发展有限公司 | A kind of method and its method for designing and purposes for improving hydrogenation reaction system hydrogen dividing potential drop |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102465011A (en) * | 2010-11-05 | 2012-05-23 | 中国石油化工股份有限公司 | Hydrotreatment method of heavy distillate 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 |
-
2013
- 2013-11-05 CN CN201310540359.3A patent/CN104611009B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102465011A (en) * | 2010-11-05 | 2012-05-23 | 中国石油化工股份有限公司 | Hydrotreatment method of heavy distillate 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104611009A (en) | 2015-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104611018B (en) | A kind of inferior raw material produces the process of lube base oil | |
| JP2015059220A (en) | Method of producing ship fuel of low sulfur content from hco produced by catalytic decomposition or slurry-type hydrocarbon-containing fraction using hydrogenation treatment stage | |
| CN104611037B (en) | A kind of inferior heavy distillate produces the method for hydrotreating of lube base oil | |
| CN103059960B (en) | Flexible hydrocracking method | |
| CN104611047B (en) | Process method for producing lubricating oil base oil through poor-quality raw material | |
| CN1202212C (en) | Heavy hydrocarbon hydroprocessing method | |
| CN104611022B (en) | A kind of inferior heavy distillate hydrocracking method | |
| CN108018084B (en) | Heavy oil hydrotreating method for improving catalyst utilization rate | |
| CN104611016B (en) | A kind of inferior raw material method for hydrogen cracking | |
| CN104611039B (en) | Inferior raw material method for hydrogen cracking | |
| CN104611009B (en) | Poor-quality heavy distillate oil hydrotreating method | |
| CN104611014B (en) | Two-stage hydrotreating method of poor-quality raw material | |
| CN104611036B (en) | A kind of height does heavy distillate oil hydrotreating method | |
| CN104611052B (en) | Inferior raw material two-stage hydrogenation processing method | |
| CN104611055B (en) | A kind of height does raw material two-stage hydrogenation processing method | |
| CN104611032B (en) | A kind of high process doing raw material production lube base oil | |
| CN104611017B (en) | Height does the method for hydrotreating of raw material production lube base oil | |
| CN104611054B (en) | A kind of high method of hydrotreating doing raw material production lube base oil | |
| CN104611024B (en) | A kind of inferior heavy distillate produces the process of lube base oil | |
| CN104611041B (en) | Inferior raw material produces the method for hydrotreating of lube base oil | |
| CN104611048B (en) | Height does raw material two-stage hydrogenation processing method | |
| CN103789021B (en) | A kind of high-nitrogen stock hydroprocessing process | |
| CN105524653B (en) | Hydrotreatment method for residual oil | |
| CN104611051B (en) | A kind of height does heavy distillate method for hydrogen cracking | |
| CN104611038B (en) | Height does the process of raw material production lube base oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |