CN107460004A - A kind of method for hydrogen cracking - Google Patents
A kind of method for hydrogen cracking Download PDFInfo
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- CN107460004A CN107460004A CN201610389925.9A CN201610389925A CN107460004A CN 107460004 A CN107460004 A CN 107460004A CN 201610389925 A CN201610389925 A CN 201610389925A CN 107460004 A CN107460004 A CN 107460004A
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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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Abstract
A kind of method for hydrogen cracking, hydrocracking raw material is contacted and reacted with Hydrobon catalyst and hydrocracking catalyst I successively in the first reaction zone, gained the first reaction zone product is after cooling, gas-liquid separation and fractionation, naphtha cut, light diesel cut, middle matter diesel oil distillate, heavier diesel fraction and tail oil fraction are obtained, middle matter diesel oil distillate obtains high-knock rating gasoline cut after further being reacted in second reaction zone.Using method provided by the invention, the quality of diesel oil can be effectively improved, taking into account reduces diesel oil density and improve the aspect of diesel cetane-number two, produces qualified or high-quality product diesel oil, also, low cost production high octane gasoline component.
Description
Technical field
It is a kind of more specifically the invention belongs to handle the method for hydrocarbon ils under conditions of it hydrogen be present
Produce the method for hydrogen cracking of diesel oil and gasoline.
Background technology
In recent years, with the deep mining of global crude oil, crude quality becomes worse and worse, relatively close
Degree and sulfur content constantly rise；And world's refined products market is towards intermediate oil (diesel oil and kerosene)
Increase in demand, the direction of the continuous reduction of demand of heavy fuel oil are developed.Therefore, oil is used as one kind not
The reproducible energy, it is adequately and reasonably to implement the important hand of resources sustainable development using its heavy distillat
Section.In China, with developing rapidly for national economy, light-weight fuel oil (especially gasoline, kerosene
And diesel oil) demand be continuously increased；Meanwhile the lifting of product quality turns into what oil refining enterprise faced
Bigger challenge.Hydrocracking technology is important oil refining enterprise's secondary operation means, can realize heavy oil
While lighting, while obtain the clean fuel for meeting environmental requirement.Therefore, development and application adds
Hydrogen cracking technology, which turns into, meets the market demand and the maximally effective means that solve the above problems.
Currently, it is corresponding with crude quality variation, charging in poor quality, the heaviness of hydrocracking unit
Degree is also constantly being deepened.One of outstanding feature that hydrocracking unit charging is deteriorated be raw material aromatic hydrocarbons and
Naphthene content amplification is obvious, and it changes the quality for influencing whether diesel oil.
New national standard is to the quality requirement more and more higher of diesel product at present, except to sulphur, nitrogen content in diesel oil
And other impurity have strict demand outer, also propose further requirement to density and Cetane number.Example
As required in GB 19147-2013, No. 5 are arrived-No. 10 diesel oil densities in 810~850kg/m3Scope, ten
Six alkane values are not less than 51；- No. 20 diesel oil densities are in 790~840kg/m3Scope, Cetane number are not less than
49；- 35 and-No. 50 diesel oil densities in 790~840kg/m3Scope, Cetane number are not less than 47.
For Petrochemical Enterprises, to pursue high yield, it is heavier, bad it is expected that hydrocracking unit can be processed
Matter wax oil cut, while also need to obtain qualified product.The characteristics of poor quality charging, is with increasingly improving
Diesel product specification generates very big contradiction.
CN101117594 discloses a kind of method of hydrotreating for producing cleaning diesel oil.By feedstock oil and circulation
Enter the second hydroconversion reaction zone after hydrogen mixing, reacted in the presence of Hydrobon catalyst,
Obtain lightweight, heavier diesel fraction, part or all of heavier diesel fraction enters the after being mixed with new hydrogen
One hydroconversion reaction zone, continue to react with catalyst for hydro-upgrading, after remaining heavy diesel fuel mixes with light diesel fuel
Diesel oil distillate as diesel product.The method of the invention handles heavier diesel fraction repeated hydrogenation, uses
In processing high-sulfur, high nitrogen and do high diesel oil distillate.
A kind of method for hydrogen cracking of selective increasing of aviation kerosene yield is disclosed in CN103013559A.Will weight
Diesel oil distillate (320~370 DEG C) returns to feedstock oil and carries out continuing to react together, wherein circulation weight bavin
The mass percent that oil distillate accounts for gross weight diesel oil distillate is 10%~100%.
US6106694 discloses a kind of method for hydrogen cracking of high-yield diesel oil.This method has a hydrogenation
Finishing reactor and a hydrocracking reactor.Virgin heavy raw material and hydrocracking reactor it is anti-
Product is answered to enter hydrofining reactor together；Hydrofining reactor effluent is carried out in fractionating column
Separation, Fractionator Bottom heavy distillat are circulated back to hydrocracking reactor and carry out cracking reaction.
The content of the invention
It is an object of the invention to provide a kind of method for hydrogen cracking, to solve in the prior art feed stock
Shoddyization, it is impossible to while diesel oil density and Cetane number property are taken into account, and gasoline fraction octane number is low
The problem of.
Method for hydrogen cracking provided by the invention, including：
(1) the first reaction zone is entered after hydrocracking raw material mixes with hydrogen-containing gas I, in the first reaction
Under area's reaction condition, contact and reacted with Hydrobon catalyst and hydrocracking catalyst I successively,
Obtain the first reaction zone product；
(2) first reaction zone products after cooling, gas-liquid separation and fractionation, obtain naphtha cut,
Light diesel cut, middle matter diesel oil distillate, heavier diesel fraction and tail oil fraction, the middle matter diesel oil
The boiling range scope of cut is 205 DEG C -300 DEG C；
(3) it is anti-to enter second after the middle matter diesel oil distillate obtained by step (2) mixes with hydrogen-containing gas II
Area is answered, under the reaction condition of second reaction zone, contacts and is reacted with hydrocracking catalyst II, obtained
To second reaction zone product；
(4) second reaction zone product obtains high-octane rating vapour after cooling, gas-liquid separation and fractionation
Oil distillate.
The present inventor has found under study for action, becomes weight with boiling range, the narrow fraction of different cut points
Linearly increasing trend is not presented in boiling range density, but the change of approximate index as shown in table 1 is presented
Change trend；In contrast, the Cetane number of the narrow fraction of different cut points is then presented as shown in table 2
The variation tendency of approximate log, moreover, both have very strong correlation and complementarity.Therefore, originally
Invention it has been recognised by the inventors that accordingly, if can optionally matter diesel oil evaporates in extraction section
Point, then can take into account diesel oil density and the aspect of Cetane number two, with less cost, obtain density it is low,
The higher product diesel oil of Cetane number number.In addition, the middle matter diesel oil distillate of extraction moderately add
Hydrogen cracking, produce high-knock rating gasoline cut.
The difference of the full cut diesel oil of table 1 fritters the density of cut
| Boiling range scope (DEG C) | 20 DEG C of density (g/mL) |
| 145-175 | 0.776 |
| 175-205 | 0.802 |
| 205-235 | 0.822 |
| 235-270 | 0.828 |
| 270-300 | 0.832 |
| 300-330 | 0.830 |
| 330-370 | 0.827 |
The difference of the full cut diesel oil of table 2 fritters the Cetane number of cut
| Boiling range scope (DEG C) | Cetane lndex |
| 145-175 | 35.5 |
| 175-205 | 39.2 |
| 205-235 | 42.8 |
| 235-270 | 53.1 |
| 270-300 | 62.2 |
| 300-330 | 75.5 |
| 330-370 | 85.0 |
According to method of the present invention, the species of the Hydrocracking Raw Oil is not limited particularly
It is fixed, under preferable case, when using method of the present invention processing Hydrocracking Raw Oil inferior, example
During such as catalytic cracking diesel oil, decompressed wax oil and wax tailings, the quality of product diesel oil is enabled to obtain
More obvious improvement.
First reaction zone product obtains naphtha cut, light after cooling, gas-liquid separation and fractionation
Matter diesel oil distillate, wherein middle matter diesel oil distillate, heavier diesel fraction and tail oil fraction, naphtha cut
Boiling range scope be C5- 145 DEG C, the boiling range scope of light diesel cut be 145~205 DEG C, middle matter bavin
The boiling range scope of oil distillate is 205~300 DEG C, the boiling range scope of heavier diesel fraction be 300~
370 DEG C, the boiling range of tail oil fraction be>370 DEG C, at least partly described middle matter diesel oil distillate is taken out, and will
The light diesel cut and heavier diesel fraction or and remainder in matter diesel oil distillate go out dress
Put, obtain product diesel oil.
Wherein, the first reaction zone reaction condition is：Reaction temperature is 320-440 DEG C, and reaction pressure is
5-20MPa, volume space velocity is 0.1-4h during liquid-1, hydrogen to oil volume ratio 400-2000:1.
In the hydrogen-containing gas I, the content of hydrogen is at least 85 volume %.
In the present invention, to the species of the Hydrobon catalyst, there is no particular limitation, can make
With the conventional use of Hydrobon catalyst for carrying out hydrofining reaction in the art.In the present invention,
Loaded before being additionally may included in the Hydrobon catalyst bed appropriate as well known to those skilled in the art
Hydrogenation pretreatment catalyst.
In first reaction zone VIII is selected from hydrocracking catalyst I containing carrier, at least one
The metallic element of race and at least one metallic element selected from group vib, contain molecular sieve in the carrier
And aluminum oxide, on the basis of the carrier, the content of molecular sieve is 3-80 weight %, and aluminum oxide contains
Measure as 20-97 weight %.
In first reaction zone in hydrocracking catalyst I, the group VIII metal element is selected from nickel
And/or cobalt, the group vib metallic element is selected from molybdenum/or tungsten, with the total of the hydrocracking catalyst
On the basis of weight, the nickel and/or cobalt using the total content that oxide is counted as 1-15 weight %, the molybdenum/
Or tungsten is using the total content that oxide is counted as 5-40 weight %；The molecular sieve be selected from y-type zeolite and/or
Beta zeolites.
In second reaction zone, boiling range scope is that 205 DEG C -300 DEG C of middle matter diesel oil distillate is urged with being hydrocracked
Agent II contacts are reacted, and obtain second reaction zone product, second reaction zone product through cooling,
After gas-liquid separation and fractionation, high-knock rating gasoline cut is obtained.
It is preferred that the reaction pressure of second reaction zone is 0.5~5MPa.
Wherein, in second reaction zone：Reaction temperature is 350-440 DEG C, and volume space velocity is 2-20h during liquid-1,
Hydrogen to oil volume ratio is 300-1300:1.
In the hydrogen-containing gas II, the content of hydrogen is at least 70 volume %, and the content of hydrogen sulfide is small
In 2 volume %.To make full use of hydrogen source, hydrogen-containing gas II of the present invention can be adding after desulfurization
Low point of gas of hydrogen production device.After described low point of gas of hydrogenation plant refers to hydrogenation plant low pressure separator gas-liquid separation
Obtained gaseous component.
Contain complex carrier in the second reaction zone in hydrocracking catalyst II and be supported on described multiple
Close the VIII non-noble metal j element and/or group vib non-noble metal j element on carrier；It is preferred that with described
On the basis of hydrocracking catalyst II gross weight, contain 50-90 in the hydrocracking catalyst II
Weight % complex carrier, the 1-10 weight % group VIII metal element and 5-40 weights in terms of oxide
Measure the % group vib metallic element in terms of oxide；Contain in more preferably described hydrocracking catalyst II
There are 60-85 weight % complex carrier, the 1.5-6.0 weight % member of the group VIII metal in terms of oxide
The group vib metallic element in terms of oxide of element and 10-35 weight %.
It is described on the basis of the gross weight of the complex carrier in the hydrocracking catalyst II
The solid acid component of aluminum oxide and 0.5-95 weight % containing 5-99.5 weight % in complex carrier；It is excellent
Select the solid acid component of the aluminum oxide and 1-80 weight % containing 20-99 weight % in the complex carrier.
The solid acid component is selected from silica-alumina and/or molecular sieve, and the molecular sieve, which is selected from, has macropore
At least one of the zeolite of structure, the zeolite with central hole structure and the zeolite with small structure.More
It is preferred that the molecular sieve is at least one of y-type zeolite, Beta zeolites and ZSM-5 zeolite.
Second reaction zone reaction effluent also obtains unconverted middle matter diesel oil and evaporated after separation and fractionation
Point, the unreacted middle matter diesel oil distillate, which is recycled to second reaction zone entrance, to be continued to react.
Tail oil fraction obtained by first reaction zone can select device, can also be recycled to the first reaction
Continue to convert in area.First reaction zone obtains light diesel cut, heavier diesel fraction, is partly introduced into
The unreacted middle matter diesel oil distillate of the middle matter diesel oil distillate of second reaction zone and part second reaction zone
Go out device after mixing.
According to method of the present invention, hydrogenation that the density ratio prior art of the product diesel oil obtains
The density of cracked diesel oil cut reduces 0.0007-0.0068g/mL；The Cetane number ratio of the product diesel oil
What prior art obtained is hydrocracked the cetane number boost 0.9-11 of diesel oil distillate.
Diesel quality low technical problem when the present invention solves hydrocracking unit raw material variation, passes through
Appropriate cutting to specific cut is simultaneously selectively extracted out so as to improve diesel quality, reaches the qualified bavin of production
The target of oil.In addition, this method coordinates suitable technique always according to the hydrocarbon compositing characteristic for extracting diesel oil out
Condition, it is further converted, obtains high octane gasoline component.
Using method provided by the invention, the quality of diesel oil can be effectively improved, it is close to take into account reduction diesel oil
Degree and the aspect of raising diesel cetane-number two, the qualified or high-quality product diesel oil of production.In addition, using
The method that the invention provides, can low cost production high octane gasoline component.
Brief description of the drawings
Accompanying drawing is the method for hydrogen cracking schematic flow sheet of production high-knock rating gasoline provided by the invention.
Embodiment
Below in conjunction with the accompanying drawings to the present invention method for hydrogen cracking be further detailed, but not because
This and limit method of the present invention.
Hydrocracking raw material 1 enters the first reaction zone 2 after being mixed with hydrogen-containing gas I, in the first reaction zone
Under reaction condition, contact and reacted with Hydrobon catalyst and hydrocracking catalyst I successively,
Obtain the first reaction zone product；First reaction zone product after cooling, gas-liquid separation and fractionation,
Obtain light naphtha fraction 3, heavy naphtha fraction 4, light diesel cut 5, middle matter diesel oil distillate 6,
Heavier diesel fraction 7 and tail oil fraction 9.The middle matter diesel oil distillate 6 of gained mixes with hydrogen-containing gas II
Enter second reaction zone 10 afterwards, under the reaction condition of second reaction zone, connect with hydrocracking catalyst II
Touch and reacted, obtain second reaction zone product；Second reaction zone product is through cooling, gas-liquid point
From with after fractionation, obtain high-knock rating gasoline cut 11 and unconverted middle matter diesel oil distillate 12, not
The middle matter diesel oil distillate 12 of reaction, which is re-circulated to second reaction zone entrance, to be continued to react.Wherein, first
The tail oil fraction 9 of reaction zone can select device, can also be recycled to the first reaction zone and continue to convert.
First reaction zone obtains light diesel cut 5, heavier diesel fraction 7, is partly introduced into second reaction zone
The unreacted middle matter diesel oil distillate 6 of middle matter diesel oil distillate 6 and part second reaction zone mix after
Go out device.
The following examples will be further described to system provided by the invention, but not because
This and limit the present invention.
The product designation RN-32V of the Hydrobon catalyst used in embodiment and comparative example, adds
Hydrogen Cracking catalyst I product designation RHC-3, hydrocracking catalyst II product designation
RHC-5.Hydrocracking raw material property is as shown in table 1.
The raw material main character of table 1
Embodiment 1
Hydrocracking Raw Oil A in reaction entrance hydrogen dividing potential drop 14.0MPa, is refined in the first reaction zone
And cracking volume space velocity difference 1.0h-1And 1.4h-1, refined and cracking reaction temperature be respectively 360 DEG C and
Contact and reacted with Hydrobon catalyst and hydrocracking catalyst I successively under conditions of 365 DEG C,
Obtain the first reaction zone product；First reaction zone product after cooling, gas-liquid separation and fractionation,
Obtain light naphtha fraction (C5-65 DEG C), heavy naphtha fraction (65-145 DEG C), light diesel cut
(145~205 DEG C), middle matter diesel oil distillate (205~300 DEG C), heavier diesel fraction (300~370 DEG C)
With tail oil fraction (>370℃).Product diesel oil is used as after light diesel cut, heavier diesel fraction mixing
Go out device, be completely drawn out entering after middle matter diesel oil distillate mixes with low point of gas of the first reaction zone after desulfurization
Second reaction zone, entrance reaction hydrogen dividing potential drop is 2MPa, 400 DEG C of reaction temperature, volume space velocity 7h-1、
Under conditions of hydrogen to oil volume ratio is 800, contacts and reacted with hydrocracking catalyst II, obtain the
Two reaction zone products, second reaction zone product obtain height after cooling, gas-liquid separation and fractionation
Octane rating gasoline fractions.Product liquid hydrocarbon product distribution in differential responses area is shown in Table 1, product diesel oil and height
The key property of octane rating gasoline fractions is shown in Table 2.
As shown in table 2, by means of the invention it is also possible to obtain the bavin that Cetane lndex reaches 64.1
Oil distillate, and production octane number reach 88 (RON) high-knock rating gasoline cut.
Table 1
| Liquid hydrocarbon product distribution/% | |
| First reaction zone | |
| C5~65 DEG C light naphtha fraction | 3.4 |
| 65~145 DEG C of heavy naphtha fractions | 17.4 |
| 145~205 DEG C of light diesel cuts | 16.5 |
| Matter diesel oil distillate in 205~300 DEG C | 20.5 |
| 300~370 DEG C of heavier diesel fractions | 13.0 |
| >370 DEG C of tail oils | 25.5 |
| Second reaction zone | |
| <205 DEG C of high-knock rating gasoline cuts | 18.3 |
| Total liquid yield | 94.1 |
Table 2
| Product | High-knock rating gasoline cut | Product diesel oil |
| Yield/% | 18.3 | 29.5 |
| Density (20 DEG C)/(g/cm3) | 0.727 | 0.8112 |
| Sulfur nutrient/(μ g/g) | <1 | <10 |
| Nitrogen content/(μ g/g) | <0.5 | <1 |
| Octane number (RON) | 88 | / |
| Cetane index | / | 64.1 |
| Freezing point/DEG C | / | <-20 |
| Smoke point/mm | / | / |
| Freezing point/DEG C | / | / |
| Flash-point/DEG C | / | >55 |
| Boiling range/DEG C | D-86 | D-86 |
| IBP | 43 | 144 |
| 10% | 68 | 163 |
| 30% | 95 | 184 |
| 50% | 120 | 292 |
| 70/% | 134 | 325 |
| 90% | 189 | 348 |
| 95% | 195 | 363 |
| FBP | 202 | 378 |
Comparative example 1
Hydrocracking Raw Oil A in reaction entrance hydrogen dividing potential drop 14.0MPa, is refined in the first reaction zone
And cracking volume space velocity difference 1.0h-1And 1.4h-1, refined and cracking reaction temperature be respectively 360 DEG C and
Under conditions of 365 DEG C, it is anti-that progress is contacted with Hydrobon catalyst and hydrocracking catalyst I successively
Should, obtain the first reaction zone product；First reaction zone product is through cooling, gas-liquid separation and fractionation
Afterwards, light naphtha fraction (C5-65 DEG C), heavy naphtha fraction (65-145 DEG C), diesel oil is obtained to evaporate
Point (145~370 DEG C) and tail oil fraction (>370 DEG C), extraction section diesel oil distillate (extracted amount with
Implementation amount is identical, the 20 weight % about fed)；Remaining diesel oil goes out device as product diesel oil.Take out
Go out after diesel oil distillate mixes with low point of gas of the first reaction zone after desulfurization to enter into the second cracking reaction area
Single step reaction.Entrance reaction hydrogen dividing potential drop is 2MPa, and diesel oil distillate is converted into gasoline fraction entirely.No
As shown in table 3, product diesel oil and high-knock rating gasoline cut with the distribution of reaction zone product liquid hydrocarbon product
Key property it is as shown in table 4.
Comparative example 1 compared with Example 1, the first reaction zone to be hydrocracked conversion level suitable, but
The diesel oil distillate of extraction is 145-370 DEG C of full cut, hydrogen dividing potential drop and conversion level in second reaction zone
It is basic quite under conditions of, low about 8 units of octane number of product gasoline；Simultaneously because remaining diesel oil
Cut fails to reject non-ideal cut, low about 8 units of Cetane lndex of product diesel oil distillate.
Table 3
| Liquid hydrocarbon product distribution/% | % |
| First cracking reaction zone | |
| C5~65 DEG C light naphtha fraction | 3.5 |
| 65~145 DEG C of heavy naphtha fractions | 17.6 |
| 145~370 DEG C of diesel oil distillates | 50.0 |
| >370 DEG C of tail oils | 25.5 |
| Second cracking reaction area | |
| <205 DEG C of high-knock rating gasoline cuts | 16.8 |
| Total liquid yield | 93.4 |
Table 4
Embodiment 2
Hydrocracking Raw Oil A in reaction entrance hydrogen dividing potential drop 15.0MPa, is refined in the first reaction zone
And cracking volume space velocity difference 1.0h-1And 1.5h-1, refined and cracking reaction temperature be respectively 380 DEG C and
Contact and reacted with Hydrobon catalyst and hydrocracking catalyst I successively under conditions of 390 DEG C,
Obtain the first reaction zone product；First reaction zone product after cooling, gas-liquid separation and fractionation,
Obtain light naphtha fraction (C5-65 DEG C), heavy naphtha fraction (65-145 DEG C), light diesel cut
(145~205 DEG C), middle matter diesel oil distillate (205~300 DEG C), heavier diesel fraction (300~370 DEG C)
With tail oil fraction (>370 DEG C), will>370 DEG C of tail oil fraction complete alternations, further turn to the first reaction zone
Change.Go out device as product diesel oil after light diesel cut, heavier diesel fraction mixing, be completely drawn out
Middle matter diesel oil distillate enters second reaction zone, entrance after being mixed with low point of gas of the first reaction zone after desulfurization
Reaction hydrogen dividing potential drop is 3MPa, 420 DEG C of reaction temperature, volume space velocity 8h-1, hydrogen to oil volume ratio 800
Under conditions of, contact and reacted with hydrocracking catalyst II, obtain second reaction zone product,
Second reaction zone product obtains high-knock rating gasoline cut after cooling, gas-liquid separation and fractionation.
Product liquid hydrocarbon product distribution in differential responses area is shown in Table 5, product diesel oil and high-knock rating gasoline cut
Key property is shown in Table 6.
As shown in table 5, by means of the invention it is also possible to obtain the bavin that Cetane lndex reaches 58.2
Oil distillate, and production octane number reach 93 (RON) high-knock rating gasoline cut.
Table 5
| Liquid hydrocarbon product distribution/% | |
| First reaction zone | |
| C5~65 DEG C light naphtha fraction | 5.5 |
| 65~145 DEG C of heavy naphtha fractions | 16.5 |
| 145~205 DEG C of light diesel cuts | 22.7 |
| Matter diesel oil distillate in 205~300 DEG C | 30.9 |
| 300~370 DEG C of heavier diesel fractions | 17.9 |
| >370 DEG C of tail oils | 2.1 |
| Second reaction zone | |
| <205 DEG C of high-knock rating gasoline cuts | 28.7 |
| Total liquid yield | 93.4 |
Table 6
Comparative example 2
Hydrocracking Raw Oil A in reaction entrance hydrogen dividing potential drop 15.0MPa, is refined in the first reaction zone
And cracking volume space velocity difference 1.0h-1And 1.5h-1, refined and cracking reaction temperature be respectively 380 DEG C and
Contact and reacted with Hydrobon catalyst and hydrocracking catalyst I successively under conditions of 390 DEG C,
Obtain the first reaction zone product；First reaction zone product after cooling, gas-liquid separation and fractionation,
Obtain light naphtha fraction (C5-65 DEG C), heavy naphtha fraction (65-145 DEG C), diesel oil distillate (145~
370 DEG C) and tail oil fraction (>370 DEG C), extraction section diesel oil distillate (extracted amount is identical with implementation amount,
The 30 weight % about fed)；Remaining diesel oil goes out device as product diesel oil,>370 DEG C of tail oil fractions are complete
Circulation.Extract out anti-into the second cracking after diesel oil distillate mixes with low point of gas of the first reaction zone after desulfurization
Area is answered further to react.Entrance reaction hydrogen dividing potential drop is 3MPa, 420 DEG C of reaction temperature, volume space velocity
8h-1, hydrogen to oil volume ratio be 800 under conditions of, diesel oil distillate is converted into gasoline fraction entirely.It is different
The distribution of reaction zone product liquid hydrocarbon product is as shown in table 7, product diesel oil and high-knock rating gasoline cut
Key property is as shown in table 8.
Comparative example 2 compared with Example 2, the first reaction zone to be hydrocracked conversion level suitable, but
The diesel oil distillate of extraction is 145-370 DEG C of full cut, hydrogen dividing potential drop and conversion level in second reaction zone
It is basic quite under conditions of, low about 7 units of octane number of product gasoline；Simultaneously because remaining diesel oil
Cut fails to reject non-ideal cut, low about 6 units of Cetane lndex of product diesel oil distillate.
Table 7
| Liquid hydrocarbon product distribution/% | % |
| First cracking reaction zone | |
| C5~65 DEG C light naphtha fraction | 5.6 |
| 65~145 DEG C of heavy naphtha fractions | 16.4 |
| 145~370 DEG C of diesel oil distillates | 72.8 |
| >370 DEG C of tail oils | 1.5 |
| Second cracking reaction area | |
| <205 DEG C of high-knock rating gasoline cuts | 27.9 |
| Total liquid yield | 92.5 |
Table 8
Claims (12)
1. a kind of method for hydrogen cracking, including：
(1) the first reaction zone is entered after hydrocracking raw material mixes with hydrogen-containing gas I, in the first reaction
Under area's reaction condition, contact and reacted with Hydrobon catalyst and hydrocracking catalyst I successively,
Obtain the first reaction zone product；
(2) first reaction zone products after cooling, gas-liquid separation and fractionation, obtain naphtha cut,
Light diesel cut, middle matter diesel oil distillate, heavier diesel fraction and tail oil fraction, the middle matter diesel oil
The boiling range scope of cut is 205 DEG C -300 DEG C；
(3) it is anti-to enter second after the middle matter diesel oil distillate obtained by step (2) mixes with hydrogen-containing gas II
Area is answered, under the reaction condition of second reaction zone, contacts and is reacted with hydrocracking catalyst II, obtained
To second reaction zone product；
(4) second reaction zone product obtains high-octane rating vapour after cooling, gas-liquid separation and fractionation
Oil distillate.
2. in accordance with the method for claim 1, it is characterised in that the first reaction zone reaction condition is：
Reaction temperature is 320-440 DEG C, reaction pressure 5-20MPa, and volume space velocity is 0.1-4h during liquid-1,
Hydrogen to oil volume ratio is 400-2000:1.
3. in accordance with the method for claim 1, it is characterised in that in the hydrogen-containing gas I, hydrogen
The content of gas is at least 85 volume %.
4. in accordance with the method for claim 1, it is characterised in that be hydrogenated with first reaction zone
Contain carrier, at least one metallic element selected from VIII and at least one choosing in Cracking catalyst I
From the metallic element of group vib, molecular sieve and aluminum oxide are contained in the carrier, using the carrier as base
Standard, the content of molecular sieve is 3-80 weight %, and the content of aluminum oxide is 20-97 weight %.
5. in accordance with the method for claim 4, it is characterised in that be hydrogenated with first reaction zone
In Cracking catalyst I, the group VIII metal element is selected from nickel and/or cobalt, the group vib metal member
Element be selected from molybdenum/or tungsten, on the basis of the gross weight of the hydrocracking catalyst, the nickel and/or cobalt with
The total content of oxide meter is 1-15 weight %, and the molybdenum/or tungsten are using the total content that oxide is counted as 5-40
Weight %；The molecular sieve is selected from y-type zeolite and/or Beta zeolites.
6. in accordance with the method for claim 1, it is characterised in that the reaction pressure of second reaction zone
For 0.5~5MPa.
7. according to the method described in claim 1 or 6, it is characterised in that in second reaction zone：Instead
It is 350-440 DEG C to answer temperature, volume space velocity 2-20h during liquid-1, hydrogen to oil volume ratio 300-1300:1.
8. in accordance with the method for claim 1, it is characterised in that in the hydrogen-containing gas II, hydrogen
The content of gas is at least 70 volume %, and the content of hydrogen sulfide is less than 2 volume %.
9. in accordance with the method for claim 1, it is characterised in that be hydrogenated with the second reaction zone
Contain complex carrier and your the non-gold of VIII being supported on the complex carrier in Cracking catalyst II
Belong to element and/or group vib non-noble metal j element；It is preferred that
On the basis of the gross weight of the hydrocracking catalyst II, in the hydrocracking catalyst II
Complex carrier containing 50-90 weight %, the 1-10 weight % member of the group VIII metal in terms of oxide
The group vib metallic element in terms of oxide of element and 5-40 weight %；More preferably
Complex carrier containing 60-85 weight % in the hydrocracking catalyst II, 1.5-6.0 weight %
Group VIII metal element in terms of oxide and 10-35 weight % the gold of the group vib in terms of oxide
Belong to element.
10. in accordance with the method for claim 9, it is characterised in that in the hydrocracking catalyst
In agent II, on the basis of the gross weight of the complex carrier, 5-99.5 weights are contained in the complex carrier
Measure % aluminum oxide and 0.5-95 weight % solid acid component；It is preferred that
The solid acid group of aluminum oxide and 1-80 weight % containing 20-99 weight % in the complex carrier
Point.
11. in accordance with the method for claim 9, it is characterised in that the solid acid component is selected from
Silica-alumina and/or molecular sieve, the molecular sieve selected from the zeolite with macroporous structure, with
The zeolite of pore structure and with small structure zeolite at least one.
12. in accordance with the method for claim 1, it is characterised in that second reaction zone reaction outflow
Thing also obtains unconverted middle matter diesel oil distillate, the unreacted middle matter bavin after separation and fractionation
Oil distillate, which is recycled to second reaction zone entrance, to be continued to react.
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