CN103131464A - Hydrocarbon catalytic conversion method for producing low carbon olefin and light aromatic hydrocarbon - Google Patents
Hydrocarbon catalytic conversion method for producing low carbon olefin and light aromatic hydrocarbon Download PDFInfo
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Abstract
A hydrocarbon catalytic conversion method for producing low carbon olefin and light aromatic hydrocarbon comprises the following steps: allowing a petroleum hydrocarbon raw material to contact with a catalytic cracking catalyst for reaction in a riser reactor, delivering reaction effluent into a fluidized bed without separation, performing oligomerization, cracking and aromatization reactions with an introduced catalyst treated by micropore modification, separating to obtain a product rich in low carbon olefin and light aromatic hydrocarbon, performing steam stripping and regeneration of the carbon deposited catalyst, dividing the carbon deposited catalyst into two parts, delivering one part to the riser reactor for recycle, delivering the other part to a catalyst micropore modification zone, contacting and reacting with a modifier, and then delivering to the fluidized bed for recycle. The method not only has high heavy oil conversion capability and high propylene selectivity for catalytic cracking of heavy hydrocarbon raw materials, but also has very good oligomerization, cracking and aromatization performance for C4-C8 olefin, and thus the purpose of increasing low carbon olefin and light aromatic hydrocarbon yield is reached.
Description
Technical field
The present invention relates to a kind of catalysis conversion method of hydro carbons, more particularly, the present invention relates to a kind of make hydrocarbons raw oil in combination type reactor catalytic cracking with the low-carbon alkene that obtains higher yields and the method for light aromatic hydrocarbons.
Background technology
The low-carbon alkene that ethene, propylene is representative of take is the most basic industrial chemicals, from the traditional method of petroleum hydrocarbon preparing low-carbon olefins, it is the steam heat cracking process, applicable raw material is the light petroleum hydrocarbons such as ethane, propane, butane, Sweet natural gas, petroleum naphtha or solar oil, and its propylene/ethylene is than demand that can not satisfying the market.And heavy oil fluid catalytic cracking also a certain amount of propylene of by-product when producing gasoline and diesel oil, but its productive rate only accounts for below 12% of stock oil.
Light aromatic hydrocarbons (benzene, toluene and dimethylbenzene are called for short BTX) is widely used in synthon, synthetic resins, synthetic rubber and various fine chemicals.At present, BTX is mainly derived from noble metal platinum reforming process and steam cracking process.
At present low-carbon alkene production is mainly usingd lighter hydrocarbons as raw material, but the shortage of raw material is day by day serious, so exploitation be take the technological line that heavy oil is raw material direct production low-carbon alkene and become trend.
USP5670037 discloses a kind of hydrocarbons catalytic conversion method of preparing low-carbon olefins, the petroleum fractions that raw material is different boiling ranges, residual oil or crude oil, in fluidized-bed or moving-burden bed reactor, use solid acid catalyst at temperature 480-680 ℃, pressure 0.12-0.4MPa, reaction times is in 0.1-6 second, carry out catalytic conversion reaction under the condition of agent-oil ratio 4-12, reacted catalyzer Returning reactor internal recycle after coke burning regeneration is used.With conventional catalytic cracking and water vapour thermal-cracking method, compare, the method can obtain more propylene and butylene.
In USP5009769, disclosed cracking hydrocarbon method adopts two riser reactor cracking hydrocarbon raw materials of different nature of carrying.Wax oil and residual oil inject the first riser tube, cracking under agent-oil ratio 5～10, the condition of 1～4 second residence time; Straight-run spirit, straight run intermediate oil and catalysis heavy petrol inject the second riser tube, cracking under agent-oil ratio 3～12, the condition of 1～5 second residence time.Two riser tube ends enter in same settling vessel, and share follow-up fractionating system.This response style is mainly for the production of high aromatic hydrocarbons stop bracket gasoline and low-carbon (LC) hydro carbons.
A kind of catalytic cracking process that increases productivity of propylene is disclosed in USP7261807.This technique enters at least part of gasoline product in second riser tube and re-starts cracking reaction, and in the catalyst composition adopted except containing macropore USY zeolite, the mineral binder bond component that also contains the mesopore zeolites such as ZSM-5 and there is cracking performance.Phosphorous in mineral binder bond component wherein, its P/Al ratio is 0.1～10.This technological process is increased low carbon olefine output significantly, particularly increases productivity of propylene.
USP7323099 discloses the two-stage catalytic cracking process that a kind of selectivity is produced low-carbon alkene.At the first reaction zone, heavy feed stock is under the catalyzed conversion containing macropore and intermediate pore molecular sieve catalyst, the gasoline component of alkene is rich in production, and the highly olefinic gasoline component that the first reaction zone generates is containing under the catalyzed conversion of intermediate pore molecular sieve catalyst at second reaction zone again, generates low-carbon alkene.
A kind of two-stage catalytic cracking process of being produced C2～C4 alkene by the heavy hydrocarbon feedstocks selectivity is disclosed in CN1299403A.Heavy feed stock, under conventional large pore zeolite catalytic cracking catalyst exists, will change into than low-boiling products in the first conversion zone be comprised of catalytic cracking unit; The generated naphtha fraction than in low-boiling products is entered in the second conversion zone, contact the generation crackate be less than the approximately zeolite catalyst of 0.7 nanometer containing about 10～50% mean pore sizes at 500～600 ℃ of temperature, wherein productivity of propylene is up to 16.8%.
A kind of catalytic cracking method is disclosed in CN102051213A.Heavy feed stock with containing cracking catalyst contact reacts in the reaction zone I of the first riser reactor that at least comprises two reaction zones of selecting the type zeolite, then reactant flow is introduced in the reaction zone II of the first riser reactor and with the cracking catalyst contact reacts of introducing reaction zone II, introducing reaction zone I is 1: 0.05～0.5 with the ratio of the cracking catalyst of reaction zone II; Gasoline fraction and/or C4 hydrocarbon are sent into to the bottom that the second riser tube adds fluidized-bed reactor and with the cracking catalyst containing selecting the type zeolite, contact and react, cracking masout is introduced bottom the second riser reactor and/or fluidized-bed reactor simultaneously.
A kind of catalyst cracking method is disclosed in CN102071054A.Heavy feed stock is sent in the first riser reactor and contacted and react with the catalyzer containing selecting the type zeolite; Gasoline fraction and/or C4 hydrocarbon are introduced to the second riser reactor, with introduce the fluidized-bed reactor of connecting with the second riser reactor and react containing selecting after type zeolite catalyst contact reacts, cracking masout is introduced to the second riser reactor and/or fluidized-bed reactor simultaneously.
A kind of hydrocarbons catalytic conversion method of producing propylene and light aromatic hydrocarbons is disclosed in CN102206509A.Heavy feed stock is sent into to the first reactor to be contacted with the cracking catalyst that contains modified beta zeolite and carries out catalytic cracking reaction, C4 hydrocarbon-fraction and/or light gasoline fraction are sent into to the second reactor and contact with the cracking catalyst that contains modified beta zeolite and carry out catalytic cracking reaction, the catalyzer after the second reactor reaction and oil gas product are introduced the 3rd reactor and are proceeded reaction.
Can increase productivity of propylene although increase catalytically cracked gasoline in aforesaid method at the catalyzed conversion of second reaction zone, but some technology has been sacrificed the Propylene Selectivity that catalytically cracked gasoline transforms, some technology is carried out not identical purposes that realizes propylene enhancing of the catalyzer of catalyzed conversion, two covering devices and regenerating unit at a set of independently device in addition again by the catalytically cracked gasoline of heavy oil catalytically cracking equipment and generation, makes complex technical process.
Summary of the invention
The objective of the invention is to propose a kind ofly to take petroleum hydrocarbon as raw material, use the catalytic cracking catalyst containing large pore zeolite and mesopore zeolite, within riser tube adds the combination type reactor that fluidized-bed forms, catalytic pyrolysis and aromatization occur under certain operational condition, the method of preparing low-carbon olefins and light aromatic hydrocarbons, it is characterized in that introducing through duct and modifying the catalytic cracking catalyst of processing in fluidized-bed reactor, oligomerisation, cracking and the aromatization of strengthening C5～C8 alkene, the productive rate of raising low-carbon alkene and light aromatic hydrocarbons.
The objective of the invention is to reach by following proposal:
(1) petroleum hydrocarbon raw material of heat is sent in the riser tube that riser tube adds the combination type reactor that fluidized-bed forms, contact catalytic cracking reaction occurs with the catalytic cracking catalyst containing large pore zeolite and mesopore zeolite of heat, reaction effluent enters fluidized-bed reactor together without separating, contact in fluidized-bed reactor and carry out oligomerisation, cracking and aromatization with the catalyzer of processing through the duct modification of introducing, the product logistics of generation and carbon deposited catalyst are through the gas-solid sharp separation;
(2) the product logistics is isolated to and comprises the dry gas that is rich in ethene, is rich in propylene and liquefied gas butylene, is rich in the gasoline fraction of light aromatic hydrocarbons;
(3) carbon deposited catalyst enters revivifier carry out coke burning regeneration under oxygen-containing gas exists after stripping;
(4) catalyzer after regeneration is divided into two portions, wherein a part time riser reactor recycles, another part is first delivered to catalyzer duct modified region and is contacted and react with the modifier that is rich in two rings and/or thrcylic aromatic hydrocarbon, thereby make its duct that produces a certain amount of coke Selective plugging catalyzer large pore zeolite on the large pore zeolite of catalytic cracking catalyst, then send to fluidized-bed reactor and recycle.
Concrete operation step of the present invention is as follows:
(1) petroleum hydrocarbon raw material is sent in the riser tube that riser tube adds the combination type reactor that fluidized-bed forms after preheating, with the catalytic cracking catalyst containing large pore zeolite and mesopore zeolite of heat, contacting, is that 480～650 ℃, reaction pressure are that 150～400 kPas, charging weight hourly space velocity are 1～200 o'clock in temperature of reaction
-1, catalyzer and raw material weight ratio (hereinafter to be referred as agent-oil ratio) be 5～25: under the condition that 1, the weight ratio of water vapour and raw material (hereinafter to be referred as water-oil ratio) is 0.05～1: 1, catalytic cracking reaction occurs, reaction effluent (comprising product logistics and carbon deposited catalyst) enters fluidized-bed reactor together without separating, contact in fluidized-bed reactor and carry out oligomerisation, cracking and aromatization with the catalyzer of modifying processing through duct, the product logistics of generation separates through gas-solid sharp separation facility with carbon deposited catalyst;
(2) the product logistics is isolated to and comprises the dry gas that is rich in ethene, is rich in propylene and liquefied gas butylene, is rich in the gasoline fraction of light aromatic hydrocarbons BTX;
(3) carbon deposited catalyst goes the stripper stripping to go out the reaction product of adsorbing on catalyzer, and the carbon deposited catalyst after stripping enters revivifier and carry out coke burning regeneration under 650～800 ℃ under the oxygen-containing gass such as air exist;
(4) catalyzer after regeneration is divided into two portions, wherein a part time riser reactor recycles, another part is first delivered to catalyzer duct modified region and is contacted with the modifier that is rich in two rings and/or thrcylic aromatic hydrocarbon, at Contact Temperature, it is 650～780 ℃, be 0.1～3 second duration of contact, under the condition that the weight ratio of modifier and petroleum hydrocarbon raw material is 0.05～0.3: 1, react, thereby make it produce the duct of a certain amount of coke Selective plugging catalyzer large pore zeolite on the large pore zeolite of catalytic cracking catalyst, sending to fluidized-bed reactor recycles again, the weight ratio of the catalytic cracking catalyst of catalyzer duct modified region and riser tube is 0.3～3: 1.
The present invention's petroleum hydrocarbon raw material used is selected from one or more in straight-run gas oil, wax tailings, deasphalted oil, hydrofined oil, hydrocracking tail oil, vacuum residuum, long residuum.
The catalytic convention design that the present invention proposes comprises combination type reactor, catalyzer duct modified region, stripper, revivifier and product separation system.Described combination type reactor is the combination type reactor consisted of a riser reactor and fluidized-bed reactor, and described catalyzer duct modified region is riser tube and/or fluidized-bed reactor.
Wherein, described riser tube be selected from the equal diameter riser reactor, etc. linear speed riser reactor and straighten one or more in the riser reactor of footpath.Described fluidized-bed reactor is selected from one or more in fixed fluidized-bed reactor, particulate fluidization bed bioreactor, bubbling bed reactor, turbulent bed reactor, fast bed reactor, transport bed reactor and dense fluidized bed bioreactor.
Described stripper is positioned at the below of described fluidized-bed reactor, and described stripper directly is communicated with the bottom of described fluidized-bed reactor, the optional position, bottom of the outlet of at least one described riser reactor and described fluidized-bed reactor is communicated with, and the entrance of the outlet of the described fluidized-bed reactor gas-solid separation equipment interior with described settling vessel is communicated with.
The catalyst regenerator of catalytic convention design of the present invention has at least two catalyst transport paths to provide hot regenerated catalyst to combination type reactor.
In the present invention, make stripper be positioned at the below of fluidized-bed reactor, and stripper is communicated with the bottom of fluidized-bed reactor.Thus, to the water vapour of supplying in stripper, can be upwards by fluidized-bed reactor, as the water filling steam of the catalytic conversion reaction wherein occurred, obtain second stage employ, be conducive to reduce the overall energy consumption of reaction.
In the preferred catalytic convention design of the present invention, and two riser reactors and fluidized-bed reactor have been used, the outlet of the first riser reactor and the bottom of this fluidized-bed reactor are communicated with, and the second riser tube is an independent riser tube, modifies as the catalyzer duct.
Stock oil contacts the generation catalytic cracking reaction with the catalytic cracking catalyst from revivifier in the first riser reactor, and the product logistics that catalytic pyrolysis produces enters fluidized-bed reactor together with carbon deposited catalyst; The product logistics contacts and carries out oligomerisation, cracking and aromatization with the catalyzer of processing through the duct modification of carbon deposited catalyst and introducing, and the product logistics of generation separates through gas-solid sharp separation facility with carbon deposited catalyst; The product logistics is isolated to and comprises the liquefied gas that is rich in low-carbon alkene, the gasoline fraction that is rich in BTX; Carbon deposited catalyst goes the stripper stripping to go out the reaction product of adsorbing on catalyzer, and the carbon deposited catalyst after stripping enters revivifier and carry out coke burning regeneration under oxygen-containing gas exists; A catalyzer part after regeneration is directly sent to the first riser reactor and is recycled, and another part is first delivered to the second riser tube and contacted with the modifier that is rich in two rings and/or thrcylic aromatic hydrocarbon under certain operational condition and react and send to fluidized-bed reactor again and recycle.
The described catalyzer duct modifier that is rich in two rings and/or thrcylic aromatic hydrocarbon is that two rings and/or thrcylic aromatic hydrocarbon content are not less than 60% compound, be selected from one or more in the derivative, phenanthrene of naphthalene, naphthalene derivatives, anthracene, anthracene, luxuriant and rich with fragrance derivative, catalytic cracking diesel oil, catalytic cracking recycle oil, steam cracking heavy gas oil, steam cracking tar, coking recycle oil, coal tar, preferred catalytic cracking heavy gas oil.
The described double activated catalytic catalyst for cracking containing large pore zeolite and mesopore zeolite, the gross weight of catalyzer of take is benchmark, it contains 1%～60% zeolite mixture, 5%～99% heat-resistant inorganic oxide and 0～70% clay.The gross weight of described zeolite mixture of take is benchmark, contains 5%～75% Y zeolite, 25%～95% the mesopore zeolite with MFI structure in described zeolite mixture.
Described can be the rare earth exchanged Y zeolite that makes of various currently known methodss, rare earth hydrogen Y zeolite, overstable gamma zeolite, hyperastable Y-type RE zeolite or two or more the mixture in them by Y zeolite.
The zeolite of the described MFI of having structure is the supersiliceous zeolite with pentasil structure, be selected from one or more in ZSM-5 and ZRP series zeolite, particularly be selected from one or more in the ZRP zeolite (CN1465527A, CN1611299A) of the ZRP zeolite (CN1211469A, CN1211470A, US6080698) of the ZRP zeolite (CN1147420A) of ZRP zeolite (CN1052290A, CN1058382A, US5232675) containing rare earth, phosphorous ZRP zeolite (CN1194181A, US5951963), phosphorous and rare earth, phosphorous and alkaline-earth metal and phosphorous and transition metal.
In addition, the zeolite of the described MFI of having structure can adopt commercially available product, also can adopt the whole bag of tricks well known in the art to be prepared, and is not repeated herein.
Described heat-resistant inorganic oxide is selected from SiO
2and/or Al
2o
3; Clay is selected from kaolin and/or halloysite.
In a preferred embodiment of hydrocarbons catalytic conversion method of the present invention, the gross weight of described hydrocarbon catalytic cracking catalyzer of take is benchmark, and described Hydrocarban coversion catalysts contains 10%～50% described zeolite mixture, 10%～70% described heat-resistant inorganic oxide and 0～60% described clay.
The present invention can use plurality of raw materials oil simultaneously, is particularly suitable for processing wax oil and/or residual oil raw material.
Compared with prior art, the present invention adopts the method that the catalyzer duct is modified, not only to the heavy hydrocarbon material catalytic, cracking has high heavy oil conversion performance and high selectivity of light olefin to make double activated catalytic catalyst for cracking containing large pore zeolite and mesopore zeolite, and C4～C8 alkene is also had to good oligomerisation, cracking and Aromatization Activity, thereby realize the purpose of low-carbon olefines high-output and light aromatic hydrocarbons.And be combined with process conditions, can also significantly reduce the productive rate of dry gas and coke.
The accompanying drawing explanation
Accompanying drawing is and the basic procedure schematic diagram of production low-carbon alkene provided by the invention with the hydrocarbons catalytic conversion method of light aromatic hydrocarbons.
Embodiment
Further illustrate method provided by the present invention below in conjunction with accompanying drawing, but the present invention is not therefore subject to any restriction.
Accompanying drawing is and the basic procedure schematic diagram of production low-carbon alkene provided by the invention with the hydrocarbons catalytic conversion method of light aromatic hydrocarbons.Wherein
1-heavy oil catalytic pyrolysis riser reactor,
11-carries the transfer lime of regenerated catalyst to riser reactor 1,
Regenerated catalyst flowrate control valve on 12-transfer lime 11,
The stock oil feed nozzle of 13-riser reactor 1,
14-riser reactor 1 outlet sparger,
2-is as the riser tube of catalyzer duct modified region,
21-carries the transfer lime of regenerated catalyst to riser tube 2,
Regenerated catalyst flowrate control valve on 22-transfer lime 21,
The modifier nozzle of 23-riser tube 2,
24-riser tube 2 outlet spargers,
The 3-fluidized-bed reactor,
The 4-settling vessel,
The 41-primary cyclone,
The 42-secondary cyclone,
The 5-stripper,
Baffle plate in 51-stripper 5,
The reclaimable catalyst transfer lime of 52-stripper 5,
Reclaimable catalyst flowrate control valve on 53-transfer lime 52,
The 6-revivifier.
Device of the present invention is the combination type reactor consisted of riser tube 1 and fluidized-bed 3, and jointly forms as the riser tube 2 of catalyzer modified region.This schematic diagram is simple flow, but this does not affect those of ordinary skills' the understanding of the present invention.
Hydrocarbon raw material is after being preheated to 180～360 ℃, spray into riser reactor 1 by nozzle 13 together with water vapour, 480～650 ℃ preferably 500～600 ℃ of temperature, pressure 0.15～0.40MPa is 0.18～0.28MPa (absolute pressure) preferably, the weight ratio of catalyzer and hydrocarbon raw material is 5～25, reaction times is 0.1～6 second preferably under the condition of 1～5 second, with the hot regenerated catalyst by from pipeline 11, contacts, reacts.Reactant flow and carbon deposited catalyst enter the bottom of fluidized-bed reactor 3 by riser tube 1 outlet sparger 14.
In preferred version of the present invention, in order to improve the productive rate of low-carbon alkene, the modifier that first will be rich in two rings and/or thrcylic aromatic hydrocarbon sprays into the bottom of riser reactor 2 by nozzle 23, with the hot regenerated catalyst from pipeline 21, contact, carry out the duct of catalyzer duct modification with the blocking catalyst large pore zeolite by the selectivity green coke, catalyzer after the duct modification is processed enters in fluidized-bed reactor 3 and contacts with the product logistics from riser tube 1, 500～650 ℃ preferably 520～600 ℃ of temperature, pressure 0.15～0.40MPa is 0.18～0.28MPa (absolute pressure) preferably, the weight ratio of catalyzer and raw material is 8～40, weight hourly space velocity 0.1～50h
-1preferred 1～20h
-1condition under carry out oligomerisation, cracking and aromatization.The reactant flow highly selective is converted into to low-carbon alkene and light aromatic hydrocarbons.
Generation is rich in low-carbon alkene and is separated with secondary cyclone 42 through primary cyclone 41 successively with reactant flow and the carbon deposited catalyst of light aromatic hydrocarbons, and reactant flow enters the product separation recovery system, and carbon deposited catalyst enters stripper 4.
Separate the reaction product obtained and further separate in the product separation recovery system, obtain being rich in the dry gas of ethene, the liquefied gas that is rich in propylene and butylene, the gasoline that is rich in light aromatic hydrocarbons, a small amount of diesel oil and heavy oil.
Separate the carbon deposited catalyst obtained and go out the hydrocarbon product of absorption with the water vapour stripping in stripper 5, deliver to revivifier 6 by pipeline 52 and regenerated, the thermocatalyst after regeneration returns to the bottom of riser tube 1 and riser tube 2 and reuses.
The following examples will be further described the present invention, but not thereby limiting the invention.The hydrocarbon raw material used in embodiment and Comparative Examples is straight-run gas oil, and its character is listed in table 1.Modifier is catalytic cracking diesel oil, and its character is listed in table 2.Catalyzer is produced by Sinopec Group's catalyzer asphalt in Shenli Refinery, and trade name is MMC-2.
Embodiment
Embodiment illustrates the effect while adopting hydrocarbon material catalytic method for transformation provided by the invention.
By catalyzer MMC-2 at 800 ℃, with 100% water vapour aging 10 hours, use medium-sized tester, in compound reactor, the loading amount of catalyzer is 60 kilograms.
In embodiment, the heavy crude hydrocarbon feed advances riser reactor 1; The modifier catalytic cracking diesel oil advances riser reactor 2 by nozzle 23.
In embodiment, agent-oil ratio refers to the weight ratio of catalyzer and fresh feed.
Operational condition and test-results are in Table 3.
Comparative Examples
Compare the effect that Comparative Examples explanation does not add modifier in identical reactor while carrying out the hydrocarbon material catalytic method for transformation with embodiment.The results are shown in Table 3.
By relatively can finding out significantly of Comparative Examples and embodiment, the low-carbon alkene of embodiment and light aromatics yield be higher than Comparative Examples all.
Although the present invention is had been described in detail by embodiment above, it is to be noted, various distortion are apparent to those skilled in the art.Therefore, these distortion should comprise in the present invention, unless these distortion have exceeded scope of the present invention.
Table 1
| Density (20 ℃), kg/m 3 | 0.8934 |
| Kinematic viscosity (80 ℃), millimeter 2/ second | 9.46 |
| Condensation point, ℃ | 36 |
| Aniline point, ℃ | 88.5 |
| Carbon residue, heavy % | 0.29 |
| Elementary composition, heavy % | |
| Carbon | 86.56 |
| Hydrogen | 12.56 |
| Sulphur | 0.18 |
| Nitrogen | 0.70 |
| Group composition, heavy % | |
| Stable hydrocarbon | 69.5 |
| Aromatic hydrocarbons | 25.1 |
| Colloid | 5.2 |
| Bituminous matter | 0.2 |
| Metal content, ppm | |
| Iron | 2.3 |
| Sodium | 1.8 |
| Nickel | 0.3 |
| Vanadium | 0.1 |
| Boiling range, ℃ | |
| Initial boiling point | 286 |
| 5％ | 335 |
| 10％ | 372 |
| 30％ | 409 |
| 50％ | 436 |
| 70％ | 460 |
| 90％ | 498 |
| 95％ | 523 |
| Final boiling point | 538 |
Table 2
| Density (20 ℃), kg/m 3 | 0.9708 |
| Boiling range, ℃ | 282～356 |
| Hydrocarbon system forms, heavy % | |
| Paraffinic hydrocarbons | 8.6 |
| Naphthenic hydrocarbon | 4.8 |
| Total aromatic hydrocarbons | 86.6 |
| Wherein, mononuclear aromatics | 5.2 |
| Double ring arene | 60.8 |
| Thrcylic aromatic hydrocarbon | 15.1 |
| The above aromatic hydrocarbons of three rings | 5.5 |
Table 3
| Embodiment | Comparative Examples | |
| Operational condition | ||
| The first riser tube 1 | ||
| Material quantity, kg/h | 6.0 | 6.0 |
| Outlet temperature of riser, ℃ | 545 | 545 |
| Agent-oil ratio, m/m | 8 | 8 |
| The residence time, second | 1.6 | 1.6 |
| Water injection rate (accounting for raw material), m% | 25 | 25 |
| The second riser tube 2 | ||
| Modify dosage, g/h | 900 | 0 |
| Outlet temperature of riser, ℃ | 600 | 600 |
| The residence time, second | 1.2 | 1.2 |
| Water filling (accounting for raw material), m% | 3 | 3 |
| The weight ratio of modifier and raw material | 0.15 | / |
| The catalyst weight ratio of riser tube 2 and riser tube 1 | 0.5 | 0.5 |
| Fluidized-bed | ||
| The bed medial temperature, ℃ | 565 | 565 |
| Agent-oil ratio, m/ |
12 | 12 |
| Weight hourly space velocity, h -1 | 2.5 | 2.5 |
| Product yield, m% | ||
| Dry gas | 8.5 | 10.2 |
| Liquefied gas | 48.6 | 44.8 |
| Gasoline | 22.6 | 23.2 |
| Diesel oil | 10.3 | 10.4 |
| Heavy oil | 2.2 | 2.4 |
| Coke | 7.5 | 8.6 |
| Loss | 0.3 | 0.4 |
| Amount to | 100 | 100 |
| Total productivity of low carbon olefin hydrocarbon, heavy % | 47.7 | 41.9 |
| Ethene | 5.6 | 4.8 |
| Propylene | 23.2 | 19.5 |
| Butylene | 18.9 | 17.6 |
| The BTX productive rate, heavy % | 14.2 | 9.6 |
Claims (8)
1. a hydrocarbons catalytic conversion method of producing low-carbon alkene and light aromatic hydrocarbons, is characterized in that the method comprises the following steps:
(1) petroleum hydrocarbon raw material of heat is sent in the riser tube that riser tube adds the combination type reactor that fluidized-bed forms, contact catalytic cracking reaction occurs with the catalytic cracking catalyst containing large pore zeolite and mesopore zeolite of heat, reaction effluent enters fluidized-bed reactor together without separating, contact in fluidized-bed reactor and carry out oligomerisation, cracking and aromatization with the catalyzer of processing through the duct modification of introducing, the product logistics of generation and carbon deposited catalyst are through the gas-solid sharp separation;
(2) the product logistics is isolated to and comprises the dry gas that is rich in ethene, is rich in propylene and liquefied gas butylene, is rich in the gasoline fraction of light aromatic hydrocarbons;
(3) carbon deposited catalyst enters revivifier carry out coke burning regeneration under oxygen-containing gas exists after stripping;
(4) catalyzer after regeneration is divided into two portions, wherein a part time riser reactor recycles, another part is first delivered to catalyzer duct modified region and is contacted and react with the modifier that is rich in two rings and/or thrcylic aromatic hydrocarbon, thereby make its duct that produces a certain amount of coke Selective plugging catalyzer large pore zeolite on the large pore zeolite of catalytic cracking catalyst, then send to fluidized-bed reactor and recycle.
2. according to the method for claim 1, it is characterized in that described petroleum hydrocarbon raw material is selected from one or more in straight-run gas oil, wax tailings, deasphalted oil, hydrofined oil, hydrocracking tail oil, vacuum residuum, long residuum.
3. according to the method for claim 1, it is characterized in that the reaction conditions of step (1) is: temperature of reaction is that 480～650 ℃, reaction pressure are that 150～400 kPas, charging weight hourly space velocity are 1～200 o'clock
-1, catalyzer and raw material weight ratio be 5～25: 1, the weight ratio of water vapour and raw material is 0.05～1: 1.
4. according to the method for claim 1, it is characterized in that the described catalyzer duct modifier that is rich in two rings and/or thrcylic aromatic hydrocarbon is that two rings and/or thrcylic aromatic hydrocarbon content are not less than 60% compound, be selected from one or more in the derivative, phenanthrene of naphthalene, naphthalene derivatives, anthracene, anthracene, luxuriant and rich with fragrance derivative, catalytic cracking diesel oil, catalytic cracking recycle oil, steam cracking heavy gas oil, steam cracking tar, coking recycle oil, coal tar.
5. according to the method for claim 1, it is characterized in that the condition that step (4) catalyzer contacts with modifier in the duct modified region is: Contact Temperature is that 650～780 ℃, duration of contact are 0.1～3 second.
6. according to the method one of in claim 1,4 and 5, the weight ratio that it is characterized in that described modifier and petroleum hydrocarbon raw material is 0.05～0.3: 1.
7. according to the method for claim 1, the weight ratio that it is characterized in that the catalytic cracking catalyst of catalyzer duct modified region and riser tube is 0.3～3: 1.
8. according to the method for claim 1, it is characterized in that described catalyzer duct modified region is riser tube and/or fluidized-bed reactor.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN104557395A (en) * | 2013-10-09 | 2015-04-29 | 中国石油化工股份有限公司 | Catalytic conversion method for production of propylene |
| CN110964559A (en) * | 2018-09-28 | 2020-04-07 | 中国石油化工股份有限公司 | Catalytic cracking method and device for producing low-carbon olefins |
| WO2022048440A1 (en) * | 2020-09-02 | 2022-03-10 | 青岛京润石化设计研究院有限公司 | Method and device for preparing propylene and ethylene by using catalytic conversion of petroleum hydrocarbons |
| CN114364454A (en) * | 2019-07-31 | 2022-04-15 | 沙特基础工业全球技术公司 | Dense phase fluidized bed reactor for maximizing BTX yield |
| CN114423845A (en) * | 2019-08-05 | 2022-04-29 | 沙特基础工业全球技术公司 | Multiple dense phase risers for maximizing aromatic hydrocarbon yield from naphtha catalytic cracking |
| CN115992007A (en) * | 2021-10-18 | 2023-04-21 | 青岛京润石化设计研究院有限公司 | Method and reactor for preparing low-carbon olefin and aromatic hydrocarbon by catalytic conversion of diesel oil and catalytic raw oil |
| CN115992004A (en) * | 2021-10-18 | 2023-04-21 | 青岛京润石化设计研究院有限公司 | Reaction method and reactor for preparing low-carbon olefin and aromatic hydrocarbon by catalytic conversion of hydrocarbon raw material as reaction raw material |
| CN115992006A (en) * | 2021-10-18 | 2023-04-21 | 青岛京润石化设计研究院有限公司 | Reaction method and reactor for preparing low-carbon olefin and aromatic hydrocarbon by fluidization catalytic conversion of hydrocarbon raw material as reaction raw material |
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| CN103664444A (en) * | 2012-09-25 | 2014-03-26 | 中国石油化工股份有限公司 | Method of producing ethylene and propylene by using waste catalytic cracking catalyst |
| CN103664444B (en) * | 2012-09-25 | 2015-10-28 | 中国石油化工股份有限公司 | A kind of method using useless catalytic cracking catalyst to produce ethene and propylene |
| CN104557395A (en) * | 2013-10-09 | 2015-04-29 | 中国石油化工股份有限公司 | Catalytic conversion method for production of propylene |
| CN104557395B (en) * | 2013-10-09 | 2016-11-02 | 中国石油化工股份有限公司 | A kind of catalysis conversion method producing propylene |
| CN110964559A (en) * | 2018-09-28 | 2020-04-07 | 中国石油化工股份有限公司 | Catalytic cracking method and device for producing low-carbon olefins |
| 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 |
| CN114364454B (en) * | 2019-07-31 | 2023-11-07 | 沙特基础工业全球技术公司 | Dense-phase fluidized bed reactor for maximizing BTX yield |
| CN114364454A (en) * | 2019-07-31 | 2022-04-15 | 沙特基础工业全球技术公司 | Dense phase fluidized bed reactor for maximizing BTX yield |
| CN114423845A (en) * | 2019-08-05 | 2022-04-29 | 沙特基础工业全球技术公司 | Multiple dense phase risers for maximizing aromatic hydrocarbon yield from naphtha catalytic cracking |
| WO2022048440A1 (en) * | 2020-09-02 | 2022-03-10 | 青岛京润石化设计研究院有限公司 | Method and device for preparing propylene and ethylene by using catalytic conversion of petroleum hydrocarbons |
| CN115992007A (en) * | 2021-10-18 | 2023-04-21 | 青岛京润石化设计研究院有限公司 | Method and reactor for preparing low-carbon olefin and aromatic hydrocarbon by catalytic conversion of diesel oil and catalytic raw oil |
| CN115992004A (en) * | 2021-10-18 | 2023-04-21 | 青岛京润石化设计研究院有限公司 | Reaction method and reactor for preparing low-carbon olefin and aromatic hydrocarbon by catalytic conversion of hydrocarbon raw material as reaction raw material |
| CN115992006A (en) * | 2021-10-18 | 2023-04-21 | 青岛京润石化设计研究院有限公司 | Reaction method and reactor for preparing low-carbon olefin and aromatic hydrocarbon by fluidization catalytic conversion of hydrocarbon raw material as reaction raw material |
| CN115992005A (en) * | 2021-10-18 | 2023-04-21 | 青岛京润石化设计研究院有限公司 | Reaction method and reactor for preparing low-carbon olefin and aromatic hydrocarbon by catalytic conversion of hydrocarbon raw material as reaction raw material |
| CN115992003A (en) * | 2021-10-18 | 2023-04-21 | 青岛京润石化设计研究院有限公司 | Method and reactor for preparing low-carbon olefin and aromatic hydrocarbon by catalytic conversion of hydrocarbon raw material as reaction raw material |
| CN116083115A (en) * | 2021-11-05 | 2023-05-09 | 青岛京润石化设计研究院有限公司 | Method and reactor for preparing low-carbon olefin and aromatic hydrocarbon by catalytic conversion of hydrocarbon raw material |
| CN116083116A (en) * | 2021-11-05 | 2023-05-09 | 青岛京润石化设计研究院有限公司 | Method and reactor for preparing low-carbon olefin and aromatic hydrocarbon by catalytic conversion of hydrocarbon reaction raw material |
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