CN106609152B - A kind of hydrocarbons catalytic conversion method of fecund butylene and light aromatic hydrocarbons - Google Patents
A kind of hydrocarbons catalytic conversion method of fecund butylene and light aromatic hydrocarbons Download PDFInfo
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- CN106609152B CN106609152B CN201510691511.7A CN201510691511A CN106609152B CN 106609152 B CN106609152 B CN 106609152B CN 201510691511 A CN201510691511 A CN 201510691511A CN 106609152 B CN106609152 B CN 106609152B
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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
- C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
- C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
- C10G55/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only including at least one catalytic cracking step
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
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- 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 the catalytic cracking fields of heavier hydrocarbon feeds, specifically disclose a kind of hydrocarbons catalytic conversion method of voluminous butylene and light aromatic hydrocarbons, and this method includes：(1) by heavier hydrocarbon feeds and first cracking catalyst haptoreaction in the first reactor, then isolated first carbon deposited catalyst and the first reaction product；(2) the light drippolene by the end point of distillation no more than 90 DEG C and the second Cracking catalyst haptoreaction in the second reactor；(3) hydro-upgrading that it is 200 390 DEG C with boiling range in third reactor that the reaction mixture obtained after reacting the second reactor is introduced directly into without isolation cracks light oil haptoreaction, then isolated second carbon deposited catalyst and the second reaction product, wherein, the hydro-upgrading cracking light oil is made by the progress hydrotreating of cracking light oil.Method according to the present invention can obtain higher butylene yield and light aromatic hydrocarbons yield.
Description
Technical field
The present invention relates to a kind of hydrocarbons catalytic conversion methods of voluminous butylene and light aromatic hydrocarbons.
Background technology
Butylene and light aromatic hydrocarbons (benzene, toluene and dimethylbenzene, abbreviation BTX) are basic industrial chemicals, and butylene mainly comes at present
It is split derived from the steam such as MTO, butane, LPG, condensate, naphtha, hydrocracking tail oil and gas-oil thermal cracking and hydrocarbon ils catalysis
Change, BTX is mainly derived from lighter hydrocarbons reforming process and steam thermal cracking process.As steam cracking uses new lightweight material, production
Product distribution will will appear variation, such as use ethane as steam crack material, with using naphtha compared with raw material, ethylene in product
Ratio significantly improves, and butylene and the yield of light aromatic hydrocarbons will reduce.In this context, heavy hydrocarbon oil catalyzed conversion is utilized
Butylene and light aromatic hydrocarbons are produced, will be an effective supplement measure of steam heat cracking ethylene preparation.
Cracking hydrocarbon method disclosed in US5009769 puies forward riser reactor cracking hydro carbons original of different nature using double
Material.Wax oil and residual oil inject first riser, cracking under conditions of oil ratio 5-10, residence time 1-4 second；Straight run vapour
Oil, straight run intermediate oil and catalysis heavy petrol inject second riser, in oil ratio 3-12, the item of residence time 1-5 second
Cracking under part.Two promote pipe end and enter in the same settler, and share subsequent fractionation system.
CN1299403A discloses a kind of by heavy hydrocarbon feedstocks selectively production C2-C4The two-stage catalytic cracking process of alkene.
This method includes：In the presence of conventional large pore zeolite catalytic cracking catalyst, in the first reaction being made of catalytic cracking unit
Heavy charge is converted to compared with low-boiling products in section.Naphtha cut in the relatively low-boiling products generated is entered by anti-
In the second conversion zone for answering area, stripping zone, catalyst regeneration zones and fractionation zone composition, at a temperature of 500-600 DEG C and containing about 10-
Zeolite catalyst of the 50 weight % average pore sizes less than about 0.7 nanometer contacts to form crackate.
US7323099 discloses a kind of two-stage catalytic cracking process of selectivity production low-carbon alkene.In the first reaction zone,
Heavy charge is under the catalyzed conversion containing macropore and intermediate pore molecular sieve catalyst, and gasoline component of the production rich in alkene, first is anti-
That answers area's generation is rich in olefinic gasoline constituents again in second reaction zone under the catalyzed conversion containing intermediate pore molecular sieve catalyst, generates
Low-carbon alkene.
CN101362961A discloses a kind of catalysis conversion method of preparing aromatic hydrocarbon and low-carbon alkene, boiling range 160-260
DEG C raw material contacted with catalytic cracking catalyst, in 450-750 DEG C of temperature, weight (hourly) space velocity (WHSV) 0.1-800h-1, reaction pressure 0.10-
The weight ratio of the weight ratio 1-150 of 1.0MPa, catalytic cracking catalyst and raw material, water vapour and raw material are the condition of 0.05-1.0
Under, cracking reaction is carried out in fluidized-bed reactor, detaches reclaimable catalyst and reaction oil gas, reclaimable catalyst return after regeneration
Reactor is returned, separation reaction oil gas is isolated to purpose product low-carbon alkene and aromatic hydrocarbons.This method ethylene, productivity of propylene and choosing
Selecting property is significantly increased, and the yield of gasoline and the yield of Aromatic Hydrocarbon in Gasoline are very high, and only a small amount of heavy oil generates, and coke yield
It is relatively low.
Although the above technology achieves obvious progress in increase catalytic cracking propylene yield aspects, increase
The limitation of catalytic cracking butylene yield is still very big, and is not directed to how to improve the yield of light aromatic hydrocarbons.
Invention content
The purpose of the present invention is overcome the existing work by heavier hydrocarbon feeds catalytic cracking producing light olefins and light aromatic hydrocarbons
Existing butylene and/or the not high defect of light aromatic hydrocarbons yield during skill, the hydro carbons for providing a kind of voluminous butylene and light aromatic hydrocarbons are urged
Change method for transformation.
To achieve the goals above, the present invention provides a kind of hydrocarbons catalytic conversion method of voluminous butylene and light aromatic hydrocarbons,
This approach includes the following steps：
(1) then isolated by heavier hydrocarbon feeds and first cracking catalyst haptoreaction in the first reactor
First carbon deposited catalyst and the first reaction product；
(2) the light drippolene by the end point of distillation no more than 90 DEG C contacts instead in the second reactor with the second Cracking catalyst
It answers；
(3) reaction mixture obtained after reacting the second reactor is introduced directly into without isolation in third reactor
The hydro-upgrading for being 200-390 DEG C with boiling range cracks light oil haptoreaction, then isolated second carbon deposited catalyst and second
Reaction product, wherein the hydro-upgrading cracking light oil carries out hydrotreating by cracking light oil and is made；
(4) first reaction product and second reaction product are fractionated, by first carbon deposited catalyst
It is stripped and is regenerated with second carbon deposited catalyst, and obtained regenerated catalyst is introduced into the first reactor and institute
It states in second reactor and recycles；
Wherein, the Cracking catalyst is the Cracking catalyst containing modified beta zeolite, and the modified beta zeolite is phosphorus and mistake
Cross the β zeolites that metal M is modified.
In the method provided by the invention, light drippolene is introduced in the second reactor and is reacted, on the one hand
It can make a small amount of carbon deposit of Cracking catalyst, covering part highly acid center, on the other hand containing a large amount of in upward reaction stream
Carbonium ion.The two aspects can be used for optimizing hydro-upgrading cracking light oil, and (hydrocracking for being especially rich in cycloalkane is light
Oil) reaction contain a large amount of carbonium ions in simultaneous reactions logistics since the highly acid center in Cracking catalyst is capped,
The hydrogen transfer reaction that hydro-upgrading cracking light oil can both have been inhibited in this way, can also quickly cause hydro-upgrading and crack light oil
Carbonium ion cracking reaction generates butylene and light aromatic hydrocarbons.Therefore, the method provided by the invention can obtain higher butylene
With light aromatic hydrocarbons yield.
Moreover, the Cracking catalyst containing modified beta zeolite used in the present invention helps to increase production butylene and light aromatic hydrocarbons.
In addition, in the present invention, in different reactors, different hydrocarbon raw materials can be used, and to different hydrocarbons
Reaction carry out subregion regulation and control so that the technique flexibility ratio of method of the invention is relatively high.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is a kind of structural schematic diagram of the embodiment for the catalytic cracking unit for implementing method of the present invention.
Reference sign
1 first reactor
11 convey the delivery pipe of regenerated Cracking catalyst to first reactor
Regenerated catalyst flow control valve in 12 delivery pipes 11
The feedstock oil feed nozzle of 13 first reactors
2 second reactors
21 convey the delivery pipe of regenerated Cracking catalyst to second reactor
Regenerated catalyst flow control valve in 22 delivery pipes 21
The light drippolene feed nozzle of 23 second reactors
The outlet distributor of 24 second reactors
3 third reactors
31 third reactor bottom hydrocracking light oil burners
32 third reactor tops cool down medium nozzle
4 strippers
41 convey the delivery pipe of reclaimable catalyst to stripper 6
The flow control valve of 42 delivery pipes 41
5 settlers
The quick disconnector of 51 first reactors
52 single stage cyclones
The thick rotation of 53 third reactors
54 single stage cyclones
6 strippers
The baffle of 61 strippers 6
The reclaimable catalyst delivery pipe of 62 strippers 6
Reclaimable catalyst flow control valve in 63 delivery pipes 62
7 regenerators
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
Herein, unless there are special explanation, term " low-carbon alkene " refers both to C2-C4 alkene, " light aromatic hydrocarbons " refer both to benzene,
Toluene and dimethylbenzene.
The voluminous butylene provided by the invention and the hydrocarbons catalytic conversion method of light aromatic hydrocarbons include：
(1) then isolated by heavier hydrocarbon feeds and first cracking catalyst haptoreaction in the first reactor
First carbon deposited catalyst and the first reaction product；
(2) the light drippolene by the end point of distillation no more than 90 DEG C contacts instead in the second reactor with the second Cracking catalyst
It answers；
(3) reaction mixture obtained after reacting the second reactor is introduced directly into without isolation in third reactor
The hydro-upgrading for being 200-390 DEG C with boiling range cracks light oil haptoreaction, then isolated second carbon deposited catalyst and second
Reaction product, wherein the hydro-upgrading cracking light oil carries out hydrotreating by cracking light oil and is made；
(4) first reaction product and second reaction product are fractionated, by first carbon deposited catalyst
It is stripped and is regenerated with second carbon deposited catalyst, and obtained regenerated catalyst is introduced into the first reactor and institute
It states in second reactor and recycles；
Wherein, the Cracking catalyst is the Cracking catalyst containing modified beta zeolite, and the modified beta zeolite is phosphorus and mistake
Cross the β zeolites that metal M is modified.
In step (1), the first reactor can be riser reactor, fluidized-bed reactor, downstriker conveying
Line reactor or the compound reactor for being passed through series connection by multiple above-mentioned reactors and/or being composed in parallel, wherein each reactor
Two or more reaction zones can be divided into as needed.Under preferable case, the first reactor is to promote tube reaction
Device.The riser reactor can be equal diameter riser reactor, etc. linear speeds riser reactor and variable diameters riser
It is one or more in reactor.
In step (1), when the first reactor is riser reactor, the reaction condition of the first reactor
May include：Temperature be 450-540 DEG C (outlet temperature of reactor), preferably 490-530 DEG C；Agent weight of oil ratio (introduces the
The catalyst of one reactor and the weight ratio of heavier hydrocarbon feeds) it is 4-15：1；The oil gas residence time is 0.1-5s, preferably 1-
4s.The absolute pressure of reaction zone can be 0.15-0.30MPa (outlet pressure of reactor), preferably 0.18-0.28MPa.
In step (1), diluent preferably is injected into the first reactor, to reduce the heavier hydrocarbon feeds
Partial pressure.The diluent can be selected from one or more in vapor, C1-C4 low-carbon alkanes and nitrogen, preferably vapor.It is dilute
The weight ratio for releasing the dosage of agent and heavier hydrocarbon feeds can be 0.01-2：1, preferably 0.05-0.20：1.
In step (2), the second reactor can be riser reactor, fluidized-bed reactor, downstriker conveying
Line reactor or the compound reactor for being passed through series connection by multiple above-mentioned reactors and/or being composed in parallel, wherein each reactor
Two or more reaction zones can be divided into as needed.Under preferable case, the second reactor is to promote tube reaction
Device.The second reactor can be a riser reactor, can also be multiple riser reactors in parallel or series.Institute
State riser reactor can be selected from equal diameter riser reactor, etc. linear speeds riser reactor and variable diameters promote tube reaction
It is one or more in device.
In a preferred embodiment, the second reactor is riser reactor, and the riser reactor
Reaction condition includes：Temperature is 540-620 DEG C (outlet temperature of reactor), and agent weight of oil ratio (introduces urging for second reactor
The weight ratio of agent and light drippolene) it is 15-100：1, the oil gas residence time is 0.1-3s.The absolute pressure of reaction zone is 0.15-
0.30MPa (outlet pressure of reactor).
It is further preferred that the riser reactor as the second reactor includes pre lift zone from top to bottom and carries
Riser, and it is provided with feed introduction, the light cracking vapour in the top of the pre-lift pipe and in the bottom of the riser
Oil is sprayed by the feed introduction in the riser.
In step (2), diluent preferably is injected into the second reactor, to reduce point of wherein hydrocarbon raw material
Pressure.The diluent can be selected from one or more in vapor, C1-C4 low-carbon alkanes and nitrogen, preferably vapor.Dilution
Agent and the weight ratio of light drippolene can be 0.01-2：1, preferably 0.05-0.20：1.
In step (2), the end point of distillation of the light drippolene is no more than 90 DEG C, preferably more than 75 DEG C, more preferably evaporates
Journey is 35-75 DEG C.The light drippolene can contain the alkene of 30-100 weight %.It is further preferred that described gently split
The olefin(e) centent solved in gasoline is not less than 45 weight %, is still more preferably not less than 55 weight %.The light drippolene can be with
Be the method for the present invention subsequent fractionation during obtained light gasoline fraction, can also be come from other cracking process, such as
Can be light FCC gasoline, steam cracking light petrol, light coker naphtha etc..Under preferable case, in the light drippolene
The light gasoline fraction obtained at least partially from the subsequent fractionation process of the method for the present invention.
In step (2), in order to further increase the yield of butylene and light aromatic hydrocarbons, it is highly preferred that the light drippolene
It is handled by selective hydrogenation before injecting the second reactor, converts alkadienes therein and alkynes to monoene
Hydrocarbon.The condition of the selection hydrotreating may include：Temperature is 20-90 DEG C, and pressure is 0.2-1MPa (absolute pressure), hydrogen and alkene
The molar ratio of hydrocarbon is 1-5：1.Used catalyst can be various conventional hydrogenation catalysts, such as nickeliferous hydrogenation catalyst
Agent, the hydrogenation catalyst can be various commercially available products, and the trade mark produced such as sinopec Chang Ling catalyst branch is RDD-1
Hydrogenation catalyst.The selective hydrogenation processing may be used conventional method and implement, such as patent application may be used
Method disclosed in CN1035775A is implemented.
In step (3), the third reactor is preferably fluidized-bed reactor.The third reactor can be one
Or multiple fluidized-bed reactors in parallel or series.The fluidized-bed reactor can be selected from dispersion fluidized bed reactor, drum
It steeps one or more in bed reactor, turbulent bed reactor, fast bed reactor and dense-phase fluidized bed reactor.
In the preferred case, the third reactor is fluidized-bed reactor, and the reaction condition of the fluidized-bed reactor
May include：Temperature be 520-600 DEG C (bed temperature), preferably 540-580 DEG C；Weight (hourly) space velocity (WHSV) is 0.2-30h-1, preferably
2-20h-1；Oil gas void tower linear speed is 0.2-1.5m/s, preferably 0.6-1.2m/s；The absolute pressure of reaction zone is 0.15-0.30MPa.
In step (3), temperature is higher when the reaction oil gas generated in third reactor leaves fluid bed bed, in order to press down
Secondary response occurs for target product processed, further preferably the cooling medium of top dilute phase space injection of the third reactor with
The upper temp of the third reactor is down to 480-540 DEG C.The cooling medium can be dry gas, vapor, thick cracking
It is one or more in gasoline and oily wastewater, most preferably oily wastewater.
In step (3), the boiling range of the hydro-upgrading cracking light oil is preferably 240-365 DEG C.The hydro-upgrading is split
Alkane and cycloalkane total content in solution light oil can be more than 70 weight %, preferably greater than 75 weight %；Two ring aromatic content
3 weight %, preferably smaller than 2 weight % can be less than；Thrcylic aromatic hydrocarbon content can be less than 1 weight %, preferably smaller than 0.5 weight
Measure %.
In step (3), the hydro-upgrading cracking light oil for injecting the third reactor is to crack light oil by adding at hydrogen
Reason is made, and aromatic hydrocarbons therein is saturated into cycloalkane.Preferably, the preparation process of hydro-upgrading cracking light oil includes：It will
Cracking light oil reaction temperature be 200-480 DEG C (preferably 300-450 DEG C), hydrogen partial pressure be 0.7-21MPa (preferably 5-16MPa),
Volume space velocity is 0.1-6h-1(preferably 0.3-2h-1), hydrogen to oil volume ratio be 100-2600 (preferably 800-1500) under conditions of into
Row hydrotreating, wherein volume space velocity is defined as the volume of the oil by unit catalyst volume in the unit interval.It should add at hydrogen
Catalyst used in reason process can contain inorganic carrier (preferably aluminium oxide or aluminium oxide-silicon oxide) and to be supported on this inorganic
At least one group VIII metal (optionally with group vi metallic combination) on carrier.The group VIII and group vi metal
It is known to the skilled person, is explicitly defined in the periodic table of elements.The content of group VIII metal is preferably 3-25 weights
Measure %, more preferably 5-15 weight %.Preferably, group VIII metal be selected from Pt, Co, Ni and Fe, be most preferably selected from Pt, Co and
Ni.Preferably, group vi metal is Mo, and content can be 5-50 weight %, preferably 10-40 weight %, more preferably 20-
30 weight %.In order to further increase the yield of butylene and light aromatic hydrocarbons, cracking light oil obtains hydro-upgrading after hydro-upgrading
Light oil is cracked, the alkane and cycloalkane total content in hydro-upgrading cracking light oil are more than 70 weight %, and preferably greater than 75
Weight %；Two ring aromatic content is less than 3 weight %, preferably smaller than 2 weight %；Thrcylic aromatic hydrocarbon content is less than 1 weight %, preferably small
In 0.5 weight %.
In step (3), the cracking light oil can be that the cracking that the subsequent fractionation of the method for the present invention obtains in the process is light
Oil can also be to come from other cracking process.Under preferable case, it is described cracking light oil at least partially from present invention side
The cracking light oil that the subsequent fractionation process of method obtains.
In a preferred embodiment, the method provided by the invention further includes：It will be from first reaction product
Distinguishing in return to step (2) and step (3) with the light drippolene and cracking light oil isolated in second reaction product makes
With even if also light the splitting of being at least partly originated from that the subsequent fractionation process of the method for the present invention obtains of the light drippolene in step (2)
Gasoline is solved, and the cracking light oil in step (3) is made at least partly to be originated from the cracking that the subsequent fractionation process of the method for the present invention obtains
Light oil.
In the method provided by the invention, light drippolene used in step (2) and weight used in step (1)
The weight ratio of matter hydrocarbon raw material can be 0.05-0.8：1, preferably 0.08-0.5：1；Hydrocracking used in step (3) is light
Oil and the weight ratio of heavier hydrocarbon feeds used in step (1) can be 0.05-0.9：1, preferably 0.08-0.6：1.
In the present invention, the heavier hydrocarbon feeds can be selected from condensate, fine and close oil, vacuum gas oil (VGO), reduced crude
With it is one or more in decompression residuum.
In method of the present invention, the second reaction that the first reaction product and step (3) that step (1) obtains obtain
Product is preferably introduced into same fractionating device and is fractionated.Fractionation obtains low-carbon alkene, gasoline, light oil, heavy oil and low point other
Sub- saturated hydrocarbons, wherein obtained light gasoline fraction can partly or entirely be back to second reactor and carry out catalytic cracking
Reaction, the obtained cracking strippings or can all be back to after hydro-upgrading in third reactor carry out instead
It answers.
In method of the present invention, the Cracking catalyst that is added in the first reactor and the second reactor
Can be identical or different, it is preferably identical.The Cracking catalyst is the Cracking catalyst containing modified beta zeolite.Preferably, with
On the basis of the total weight of the Cracking catalyst, the Cracking catalyst contains the zeolite mixture of 1-60 weight %, 5-99 weights
Measure the clay of the heat-resistant inorganic oxide and 0-70 weight % of %；It is highly preferred that the Cracking catalyst contains 10-50 weight %
Zeolite mixture, 10-70 weight % heat-resistant inorganic oxide and 0-60 weight % clay.Wherein, mixed with the zeolite
On the basis of the total weight for closing object, modified beta zeolite that the zeolite mixture contains 1-75 weight % and 25-99 weight %'s has
The zeolite of MFI structure；It is highly preferred that the zeolite mixture contains the modified beta zeolite and 30-90 weight % of 10-70 weight %
The zeolite with MFI structure.
In the present invention, the modified beta zeolite is phosphorus and the β zeolites that transition metal M is modified.The modified beta zeolite can be adopted
It is prepared with various conventional methods, for example, phosphorus and transition metal M can be introduced during synthesizing β zeolites, or is being closed
At after β zeolites using ammonium exchange, P Modification, transition metal M be modified and calcination process and etc. introduce phosphorus and transition gold
Belong to M.The transition metal M can be in Fe, Co, Ni and Cu one or more, preferably Fe and/or Cu.
In the present invention, the zeolite with MFI structure can be the silica-rich zeolite with pentasil structures, be selected from
It is one or more in ZSM-5 and ZRP series zeolites.Preferably, the zeolite with MFI structure is the ZRP zeolites (ginseng containing rare earth
See CN1052290A, CN1058382A, US5232675), phosphorous ZRP zeolites (referring to CN1194181A, US5951963), contain
The ZRP zeolites (referring to CN1147420A) of phosphorus and rare earth, phosphorous and alkaline-earth metal ZRP zeolites (referring to CN1211469A,
CN1211470A, US6080698) and the ZRP zeolites (referring to CN1465527A, CN1611299A) of phosphorous and transition metal in
It is one or more.
Commercially available product may be used in the β zeolites and the zeolite with MFI structure, can also use well known in the art
Prepared by various methods, details are not described herein.
In the present invention, the heat-resistant inorganic oxide can be selected from SiO2And/or Al2O3。
In the present invention, the clay can be various clays commonly used in the art, as kaolin and/or more water are high
Ridge soil.
In the present invention, the hydrocarbons catalytic conversion method can also include evaporating the gasoline of obtained catalytic pyrolysis entirely
Gasoline fraction of the boiling range between 70-180 DEG C (preferably between 80-170 DEG C) after dividing or being cut (is rich in the vapour of aromatic hydrocarbons
Oil ingredient) hydrofinishing obtains treated gasoline；Then treated gasoline is subjected to solvent extraction, obtains the step of benzene,toluene,xylene
Suddenly.The hydrofinishing may be used conventional method and implement, and usually may include by the gasoline fraction and hydrogenation catalyst
And hydrogen contact, hydrogen partial pressure is 2.0-15.0MPa, temperature is 200-400 DEG C, hydrogen to oil volume ratio 100-1000：1, body
Product air speed is 0.5-5h-1Under conditions of react, be saturated alkene, alkadienes and alkynes therein, while removing the impurity such as sulphur nitrogen, obtain
To treated gasoline.The hydrogenation catalyst can be the Section VI B and/or VIII being supported on aluminium oxide and/or amorphous silicon aluminium
Race's non-precious metal catalyst, the Section VI B base metals can be selected from Mo or/and W, and the group VIII base metal can select
From Co or/and Ni (referring to CN1109495A, CN1631529A, CN1631526A, CN1632071A).Preferably, described plus hydrogen
Catalyst contains the additive of 0-10 weight %, at least one group VIII metal of 1-9 weight %, 12-39 weight % extremely
A kind of few vib metals and aluminium oxide and/or amorphous silicon aluminium carrier, wherein the additive can be selected from fluorine, phosphorus etc.
The metallic elements such as nonmetalloid and titanium.
Conventional method, which may be used, in the solvent extraction implements, such as may include the refined vapour for obtaining hydrofinishing
Oil is contacted with solvent, is extracted, is obtained under conditions of temperature is 80-120 DEG C, the volume ratio between solvent and treated gasoline is 2-6
To benzene,toluene,xylene (referring to patent CN1393507A, CN1258717A).Wherein, the solvent of solvent extraction can be selected from ring
Fourth sulfone, N-Methyl pyrrolidone, diethylene glycol ether, triethylene glycol ether, tetraethylene glycol, dimethyl sulfoxide (DMSO) and N- formyl-morpholine ethers
In it is one or more, can be recycled after solvent recovery.I.e. non-aromatics of raffinating oil can be used as steam crack material, can also
Introduce catalyst cracker carry out cracking reaction, such as can introduce first reactor, second reactor, third reactor into
Row cracking reaction, can be also used for blended gasoline.
The low-carbon olefines high-output provided by the invention and the hydrocarbons catalytic conversion method of light aromatic hydrocarbons can be shown in Fig. 1
Implement in catalytic cracking unit, specifically, the catalytic cracking unit include the first riser reactor 1 (i.e. first reactor),
Second riser reactor 2 (i.e. second reactor) and fluidized-bed reactor 3 (i.e. third reactor), second riser are anti-
Device 2 is answered to be located at the lower section of the fluidized-bed reactor 3, first riser reactor 1, the third fluidized-bed reactor 3
With 6 three device laid out in parallel of the settler.Moreover, by spraying into cooling medium in the dilute phase space of third reactor, it can be quick
Reaction oil gas is cooled down, and quickly draws reactor, to which the reaction oil gas residence time be greatly decreased, avoids the target generated production
Object (i.e. butylene hydrocarbon and light aromatic hydrocarbons) further consumes, while can be substantially reduced dry gas yied.
In the preferred case, as shown in Figure 1, the catalytic cracking unit for implementing the method for the present invention includes：First riser
Reactor 1, the second riser reactor 2, fluidized-bed reactor 3, settler 5 and stripper 4 and 6, the stripper 4 are located at institute
The lower section of fluidized-bed reactor 3 is stated, the stripper 6 is located at the lower section of settler 5.The outlet 24 of second riser reactor 2
Be connected to the lower part any position of the fluidized-bed reactor 3, and the fluidized-bed reactor 3 and settler 5 by one or
Plurality of passages are connected to.It is highly preferred that stripper 4 and fluidized-bed reactor 3 are coaxial, and positioned at the lower section of fluidized-bed reactor 3, vapour
Device 4 is carried to be connected to by one or more channel with stripper 6.Wherein, the first riser reactor 1 and the second riser reactor
2 are selected from the combination that isodiametric pipe, taper type cylinder or the different straight barrel of 1-6 sections of diameters are formed by connecting by reducer
At least one of body；The fluidized-bed reactor 3 is selected from isodiametric cylinder, taper type cylinder or different straight of 1-6 sections of diameters
At least one for the assembly that cylinder is formed by connecting by reducer.
The catalytic cracking unit can also include regenerator 7, and the carbon deposited catalyst after stripping is logical by catalyst transport
Road 62 is delivered to regenerator 7 under the control of reclaimable catalyst flow control valve 63；Regenerated Cracking catalyst can be by defeated
It send pipe 11 to be delivered to the first riser reactor 1 under the control of regenerated catalyst flow control valve 12, conveying can also be passed through
Pipe 21 is delivered to the first riser reactor 2 under the control of regenerated catalyst flow control valve 22, to urge regenerated cracking
Agent is recycled.
Below in conjunction with Fig. 1 to the hydrocarbons catalytic conversion method of the voluminous butylene provided by the invention and light aromatic hydrocarbons into traveling
One step illustrates, but is not intended to limit the present invention.
A kind of specific implementation mode that the catalytic cracking unit for implementing the method for the present invention is shown in Fig. 1, although the signal
Figure is simple flow, but this has no effect on those skilled in the art's the understanding of the present invention.Specifically, the catalytic cracking unit packet
Including riser reactor 1 (first reactor), riser reactor 2 (second reactor), fluidized-bed reactor 3, (third is reacted
Device), stripper 4, settler 5, stripper 6 and regenerator 7.Settler 4 and stripper 6 are coaxial, and wherein stripper 6 is located at sedimentation
The lower section of device 5.Stripper 4, riser reactor 2 and fluidized-bed reactor 3 are coaxial, and wherein stripper 4 is located at fluidized-bed reaction
The lower section of device 3, the outlet of riser reactor 2 are connected to the bottom any position of fluidized-bed reactor 3.Riser reactor 1
End be connected to the entrance of quick disconnector 51, the end of fluidized-bed reactor 3 is connected to the entrance of quick disconnector 53.Vapour
Device 4 is carried to be connected to stripper 6 by channel 41.The catalyst material position of fluidized-bed reactor 3 passes through catalyst flow control valve 42
Aperture be adjusted.
After heavier hydrocarbon feeds are preheated to 180-340 DEG C, riser reactor is sprayed by nozzle 13 together with vapor
1, temperature be 450-540 DEG C (preferably 490-530 DEG C), absolute pressure be 0.15-0.30MPa (being preferably 0.18-0.28MPa),
Under conditions of the weight ratio of catalyst and heavier hydrocarbon feeds is 4-15, the oil gas residence time is 0.1-5s (preferably 1-4s),
It contacts and reacts with the Regenerated cracking catalyst by the heat from pipeline 11.Reaction stream and catalyst pass through 51 He of fast separating device
Single stage cyclone 52 detaches, and the carbon deposited catalyst of separation enters stripper 6, and isolated reaction oil gas logistics, which introduces, to divide
Distillation unit.
Light drippolene from fractionating device of the present invention is 0.15-0.3MPa, agent in 540-620 DEG C, reaction zone absolute pressure
Weight of oil ratio is 15-100：1, the oil gas residence time be 0.1-3s under conditions of urged in the lower part of riser reactor 2 and cracking
Agent is contacted and is reacted.Cracking light oil from fractionating device of the present invention after hydro-upgrading, 520-600 DEG C, quickly
The entrance of separator 51 is connected to, and reaction zone absolute pressure is 0.15-0.30MPa, injects the bottom of fluidized-bed reactor 3, and from the
The reaction was continued in fluidized-bed reactor 3 together for the reaction mixture of two reactors.In order to improve the yield of butylene and light aromatic hydrocarbons,
(end point of distillation is no more than 85 DEG C to the light pyrolysis gasoline cut fraction rich in alkene that the present invention preferably obtains fractionating device, preferably 70-
75 DEG C), reaction temperature is 20-90 DEG C, the molar ratio of absolute pressure 0.2-1MPa, hydrogen and alkene is 1-5：Under conditions of 1,
On nickel-containing catalyst after selective hydrogenation converts alkadienes and alkynes to alkene, riser is sprayed by nozzle 23
2 bottom of reactor contacts and reacts with the Regenerated cracking catalyst of the heat from pipeline 21.The position of nozzle 23 is located at riser
The top of the pre lift zone of reactor 2.The cracking light oil that the present invention further preferably obtains fractionating device is 300- in reaction temperature
450 DEG C, hydrogen partial pressure 5-16MPa, volume space velocity 0.3-2h-1, hydrogen to oil volume ratio 800-1500：Added under conditions of 1
Hydrogen processing, double ring arene therein and thrcylic aromatic hydrocarbon are saturated, and the middle matter hydrocarbon raw material after hydrotreating is sprayed by nozzle 31
The bottom of fluidized-bed reactor 3 (is preferably for 520-600 DEG C in temperature together with the reaction stream from riser reactor 2
540-590 DEG C), absolute pressure be 0.15-0.30MPa (preferably 0.18-0.28MPa), weight (hourly) space velocity (WHSV) 0.2-30h-1(preferably 2-
20h-1), oil gas void tower linear speed reacts under conditions of being 0.2-1.5m/s (preferably 0.6-1.2m/s).In fluidized-bed reactor 3
After interior reaction, the oil gas for carrying partial catalyst enters quick disconnector 53 and single stage cyclone 54, catalyst and oil gas
Separation, catalyst enter stripper 6, and the oil gas of separating liquiding catalyst enters fractionating device.Fractionating device obtain gas (including
Carbon dioxide, carbon monoxide, dry gas and liquefied gas), light petrol, be rich in light aromatic hydrocarbons heavy petrol, diesel oil and heavy oil.Gas products are logical
Isolation technics well known to those skilled in the art is crossed, the low-carbon alkenes such as propylene, butylene are obtained.Reclaimable catalyst is in stripper, and 6
The hydrocarbon product of absorption is stripped off in (being provided with baffle 61), is sent to regenerator 7 and is regenerated by pipeline 62, it is hot after regeneration
Regenerated cracking catalyst back to riser reactor reuse.
Temperature is also very high when reaction oil gas leaves fluid bed bed, to inhibit target product that secondary response occurs, passes through spray
Mouth 32 sprays into cooling medium oily wastewater in the dilute phase space of fluid bed, and reaction oil gas temperature is down to 480-540 DEG C.
The following examples will be further described this method, but be not intended to limit the present invention.
Following embodiment carries out on medium-sized tester, flow as shown in Figure 1, wherein riser reactor 1 it is interior
Diameter (diameter) is 18 millimeters, and 6 meters of height, the internal diameter (diameter) of riser reactor 2 is 12 millimeters, 5 meters of height, fluidized-bed reaction
64 millimeters of the internal diameter in 3 exit of device, 0.2 meter~0.5 meter of height, 300 millimeters of settler internal diameter.
Embodiment 1
The Cracking catalyst used in the present embodiment is：On the basis of the total weight of Cracking catalyst, cracking catalysis used
Agent contains the kaolin and 25 weights of the β zeolites of 10 weight %, the ZSM-5 zeolite (silica alumina ratio 40) of 20 weight %, 45 weight %
Measure the alumina binder of %, wherein the phosphorus containing the iron of 1 weight % and 1.5 weight % based on the element in β zeolites.Cracking catalysis
Agent aging 10 hours under 800 DEG C, 100% water vapour atmosphere, the loading amount (system catalyst reserve) of catalyst is 60 in device
Kilogram.
Heavier hydrocarbon feeds (its property is as shown in table 1) are introduced into riser reactor 1, are urged with the heat from regenerator 7
After agent haptoreaction, reaction oil gas is detached with catalyst, and reaction oil gas leaves reactor and introduces fractionating device, isolated
Carbon deposited catalyst introduces stripper 6, and regenerator 7 is transported to after stripping and is regenerated, and reaction oil gas introduces fractionating system；Gently
Pyrolysis gasoline cut fraction (composition is shown in Table 2, the light petrol boiling range be 35-75 DEG C) introduces the bottom of riser reactor 2, and from again
The thermocatalyst haptoreaction of raw device；(composition is shown in Table 3 to the cracking light oil distillate of hydro-upgrading, which is
240-365 DEG C) injection bed reactor 3 bottom, contacted instead with catalyst together with from the reaction oil gas of second reactor
It answers, oil gas and catalyst are by the outlet of fluidized-bed reactor 3, and by sedimentation, most of catalyst falls into fluid bed bed.And
The oil gas for carrying partial catalyst enters quick disconnector 53 and single stage cyclone 54, catalyst and Oil-gas Separation, carbon deposit
Catalyst enters stripper 6, and the oil gas of separating liquiding catalyst enters fractionating device.Carbon deposited catalyst is transported to again after stripping
Raw device is regenerated.Introduce the light drippolene amount of riser reactor 2 and the heavier hydrocarbon feeds for introducing riser reactor 1
Weight ratio be 0.15, introduce the hydro-upgrading cracking light oil distillate of fluidized-bed reactor 3 and introduce riser reactor 1
The weight ratio of heavier hydrocarbon feeds is 0.15, and reaction condition and reaction result are shown in Table 4.
Embodiment 2
The flow of the present embodiment and the Cracking catalyst that uses with embodiment 1, unlike, light drippolene (be shown in by property
Table 2) in 40 DEG C of reaction temperature, reaction pressure 0.5MPa, hydrogen and alkene molar ratio be 4：Under 1, (it is purchased from hydrogenation catalyst
Sinopec Chang Ling catalyst branch, trade mark RDD-1) on pass through selective hydrogenation, alkadienes and alkynes are converted into
Riser reactor 2 is introduced after monoolefine, remaining reaction condition and reaction result are shown in Table 4.
Comparative example 1
The reaction unit is traditional DCC type of reactor, i.e. riser+bed reactor, riser reactor is located at
The lower section of fluidized-bed reactor.Heavier hydrocarbon feeds (its property is as shown in table 1) are introduced into riser reactor 1, and from again
It is anti-that the thermocatalyst haptoreaction light gasoline fraction (composition is shown in Table 2, which is 35-75 DEG C) of raw device introduces riser
The middle part for answering device, with the thermocatalyst haptoreaction from upstream；(composition is shown in Table 3 to the cracking light oil distillate of hydro-upgrading, the bavin
Oil distillate boiling range be 240-365 DEG C) introduce fluidized-bed reactor 3 bottom, with catalyst haptoreaction；Reaction oil gas and catalysis
Agent introduces fluidized-bed reactor, and the reaction was continued, and oil gas and catalyst pass through the outlet of fluidized-bed reactor, and oil gas enters settler,
The catalyst wherein carried, catalyst and Oil-gas Separation are separated by two stage cyclone separator, carbon deposited catalyst enters stripping
The oil gas of device, separating liquiding catalyst enters fractionating device.Carbon deposited catalyst is transported to regenerator after stripping and is regenerated.Draw
Enter the light drippolene total amount of riser reactor and the weight ratio for the heavier hydrocarbon feeds for introducing riser reactor 1 is
0.15, introduce the hydrocracking fraction of fluidized-bed reactor and the heavier hydrocarbon feeds for introducing riser reactor 1 weight it
Than being 0.15, reaction condition and reaction result are shown in Table 5.
Embodiment 3
The flow of the present embodiment with embodiment 1, unlike, the Cracking catalyst used is：With the total of Cracking catalyst
On the basis of weight, Cracking catalyst used contain the β zeolites of 15 weight %, 15 weight % ZSM-5 zeolite (silica alumina ratio 40),
The alumina binder of the kaolin of 45 weight % and 25 weight %, wherein in β zeolites containing the iron of 1 weight % based on the element and
The phosphorus of 1.5 weight %；Moreover, reaction condition and reaction result are shown in Table 6.
Embodiment 4
The flow of the present embodiment with embodiment 1, unlike, the cooling medium (water of injection on the top of fluidized-bed reactor 3
Steam), the temperature that fluid bed is exported to reaction oil gas is reduced to 490 DEG C；Moreover, reaction condition and reaction result are shown in Table 6.
Table 1
Table 2
| Light pyrolysis gasoline cut fraction composition | Weight % |
| Alkane | 32 |
| Alkene | 61 |
| Cycloalkane | 3 |
| Aromatic hydrocarbons | 2 |
| Alkadienes and alkynes content | 2 |
Table 3
| The cracking light oil distillate of hydro-upgrading forms | Weight % |
| Alkane | 23.5 |
| One cycloalkane | 9.5 |
| Bicyclic alkane | 45.7 |
| Three cycloalkane | 9.7 |
| Total cycloalkane | 64.9 |
| Alkylbenzene | 4.8 |
| Indane or naphthane | 3.9 |
| Indene | 1.5 |
| Total mononuclear aromatics | 10.2 |
| Naphthalene | 0.2 |
| Naphthalenes | 0.6 |
| Acenaphthene class | 0.3 |
| Acenaphthylene class | 0.1 |
| Total double ring arene | 1.2 |
| Thrcylic aromatic hydrocarbon | 0.2 |
| Total weight | 100 |
Table 4
Table 5
Table 6
* in table 4-6, A refers to riser reactor 1, and B refers to riser reactor 2, and C refers to fluidized-bed reactor 3.
* in table 4-6, oil ratio refers to the weight ratio of catalyst and reactor feed.Material balance is with heavy hydrocarbon original
It being calculated on the basis of material, butylene yield is obtained with the weight of butylene weight divided by heavier hydrocarbon feeds in product,
Light aromatic hydrocarbons yield is obtained with the weight of light aromatic hydrocarbons weight divided by heavier hydrocarbon feeds in product.
* in table 4-6, reaction pressure refers to settler outlet pressure.
By the data of table 4-6 as it can be seen that method according to the present invention can obtain higher butylene yield and light aromatic hydrocarbons
Yield.
Claims (26)
1. a kind of hydrocarbons catalytic conversion method of fecund butylene and light aromatic hydrocarbons, this approach includes the following steps：
(1) by heavier hydrocarbon feeds and first cracking catalyst haptoreaction in the first reactor, then isolated first
Carbon deposited catalyst and the first reaction product；
(2) the light drippolene by the end point of distillation no more than 90 DEG C and the second Cracking catalyst haptoreaction in the second reactor；
(3) reaction mixture obtained after reacting the second reactor is introduced directly into third reactor and evaporates without isolation
The hydro-upgrading that journey is 240-365 DEG C cracks light oil haptoreaction, then isolated second carbon deposited catalyst and the second reaction
Product, wherein the hydro-upgrading cracking light oil carries out hydrotreating by cracking light oil and is made, and the hydro-upgrading cracks light oil
In alkane and cycloalkane total content be more than 70 weight %, two ring aromatic content is less than 3 weight %, and thrcylic aromatic hydrocarbon content is less than
1 weight %；
(4) first reaction product and second reaction product are fractionated, by first carbon deposited catalyst and institute
It states the second carbon deposited catalyst to be stripped and regenerated, and obtained regenerated catalyst is introduced into the first reactor and described the
It is recycled in two reactors；
Wherein, the Cracking catalyst is the Cracking catalyst containing modified beta zeolite, and the modified beta zeolite is phosphorus and transition gold
Belong to the β zeolites that M is modified.
2. according to the method described in claim 1, wherein, in step (1), the first reactor is riser reactor,
The reaction condition of the first reactor includes：Temperature is 450-540 DEG C, and agent weight of oil ratio is 4-15：1, the oil gas residence time
For 0.1-5s.
3. according to the method described in claim 1, wherein, in step (2), the second reactor is riser reactor,
The reaction condition of the second reactor includes：Temperature is 540-620 DEG C, and agent weight of oil ratio is 15-100：1, when oil gas stops
Between be 0.1-3s.
4. according to the method described in claim 3, wherein, the riser reactor as the second reactor wraps from top to bottom
Pre lift zone and riser are included, and charging spray is provided in the top of the pre-lift pipe and in the bottom of the riser
Mouth, the light drippolene are sprayed by the feed introduction in the riser.
5. according to the method described in any one of claim 1,3 and 4, wherein in step (2), the light drippolene
The end point of distillation be no more than 75 DEG C.
6. according to the method described in claim 5, wherein, the boiling range of the light drippolene is 35-75 DEG C.
7. according to the method described in claim 5, wherein, the olefin(e) centent in the light drippolene is 30-100 weight %.
8. according to the method described in claim 7, wherein, the olefin(e) centent in the light drippolene is 45-100 weight %.
9. according to the method described in any one of claim 1 and 3-4, wherein in step (2), the light drippolene
It is handled by selective hydrogenation before injecting the second reactor.
10. according to the method described in claim 9, wherein, the process of the selective hydrogenation processing includes：By the light cracking
Gasoline is temperature is 20-90 DEG C, the molar ratio of absolute pressure 0.2-1MPa, hydrogen and alkene is 1-5：Under conditions of 1, urged nickeliferous
Selective hydrogenation is carried out in the presence of agent.
11. according to the method described in claim 1, wherein, in step (3), the third reactor is fluidized-bed reactor,
The reaction condition of the third reactor includes：Temperature is 520-600 DEG C, weight (hourly) space velocity (WHSV) 0.2-30h-1, oil gas void tower linear speed
For 0.2-1.5m/s.
12. according to the method for claim 11, wherein the weight (hourly) space velocity (WHSV) in the third reactor is 2-20h-1。
13. according to the method for claim 11, wherein the oil gas void tower linear speed in the third reactor is 0.6-
1.2m/s。
14. according to the method described in any one of claim 1 and 11-13, wherein further include described in step (3)
The cooling medium of top dilute phase space injection of third reactor by the upper temp of the third reactor to be down to 480-540
℃。
15. according to the method for claim 14, wherein the cooling medium is dry gas, vapor, raw pyrolysis gasoline and contains
It is one or more in oily water.
16. according to the method for claim 15, wherein the cooling medium is oily wastewater.
17. according to the method described in any one of claim 1 and 11-13, wherein in step (3), the hydro-upgrading
The alkane and cycloalkane total content cracked in light oil is more than 75 weight %, and two ring aromatic content is less than 2 weight %, thrcylic aromatic hydrocarbon
Content is less than 0.5 weight %.
18. according to the method described in claim 1, wherein, in step (3), the hydro-upgrading cracks the preparation of light oil
Journey includes：Will cracking light oil reaction temperature be 200-480 DEG C, hydrogen partial pressure 0.7-21MPa, volume space velocity 0.1-6h-1, hydrogen
Oil volume ratio is 100-2600：Hydrotreating is carried out under conditions of 1.
19. according to the method described in claim 1, wherein, light drippolene used in step (2) with it is used in step (1)
Heavier hydrocarbon feeds weight ratio be 0.05-0.8：1；It is used in hydrocracking light oil used in step (3) and step (1)
Heavier hydrocarbon feeds weight ratio be 0.05-0.9：1.
20. according to the method for claim 19, wherein used in light drippolene used in step (2) and step (1)
Heavier hydrocarbon feeds weight ratio be 0.08-0.5：1.
21. according to the method for claim 19, wherein hydrocracking light oil used in step (3) and institute in step (1)
The weight ratio of heavier hydrocarbon feeds is 0.08-0.6：1.
22. according to the method described in any one of claim 1 and 19-21, wherein the heavier hydrocarbon feeds are decompression watt
At least one of this oil, reduced crude and decompression residuum.
23. according to the method described in any one of claim 1-4, wherein the method further includes：It will be anti-from described first
Answer the light drippolene isolated in product and second reaction product and cracking light oil difference return to step (2) and step
(3) it is used in.
24. according to the method described in claim 1, wherein, the Cracking catalyst contain 1-60 weight % zeolite mixture,
The clay of the heat-resistant inorganic oxide and 0-70 weight % of 5-99 weight %, wherein the total weight with the zeolite mixture is
Benchmark, the zeolite mixture contain the zeolite with MFI structure of the modified beta zeolite and 25-99 weight % of 1-75 weight %.
25. according to the method for claim 24, wherein transition metal M in the modified beta zeolite be selected from Fe, Co, Ni and
At least one of Cu.
26. according to the method for claim 24, wherein the transition metal M in the modified beta zeolite is selected from Fe and/or Cu.
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| CN110551520B (en) * | 2018-05-30 | 2021-10-08 | 中国石油化工股份有限公司 | Catalytic cracking method for producing clean gasoline |
| CN110551519B (en) * | 2018-05-30 | 2021-12-17 | 中国石油化工股份有限公司 | Catalytic cracking method for producing propylene and light aromatic hydrocarbon |
| CN110964559B (en) * | 2018-09-28 | 2022-04-12 | 中国石油化工股份有限公司 | Catalytic cracking method and device for producing low-carbon olefins |
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| CN102071054A (en) * | 2009-10-30 | 2011-05-25 | 中国石油化工股份有限公司 | Catalytic cracking method |
| CN104560149A (en) * | 2013-10-16 | 2015-04-29 | 中国石油化工股份有限公司 | Hydrocarbon catalytic conversion method of productive butene |
| CN104560154A (en) * | 2013-10-16 | 2015-04-29 | 中国石油化工股份有限公司 | Hydrocarbon catalytic conversion method of productive low-carbon olefin and light aromatic hydrocarbon |
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| GB593041A (en) * | 1945-03-28 | 1947-10-07 | Standard Oil Dev Co | Improvements in the catalytic conversion of hydrocarbon oils to obtain gasoline |
| CN102071054A (en) * | 2009-10-30 | 2011-05-25 | 中国石油化工股份有限公司 | Catalytic cracking method |
| CN104560149A (en) * | 2013-10-16 | 2015-04-29 | 中国石油化工股份有限公司 | Hydrocarbon catalytic conversion method of productive butene |
| CN104560154A (en) * | 2013-10-16 | 2015-04-29 | 中国石油化工股份有限公司 | Hydrocarbon catalytic conversion method of productive low-carbon olefin and light aromatic hydrocarbon |
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