CN107974282A - It is a kind of to produce low-carbon alkene and the catalytic cracking method of light aromatic hydrocarbons - Google Patents

It is a kind of to produce low-carbon alkene and the catalytic cracking method of light aromatic hydrocarbons Download PDF

Info

Publication number
CN107974282A
CN107974282A CN201610920146.7A CN201610920146A CN107974282A CN 107974282 A CN107974282 A CN 107974282A CN 201610920146 A CN201610920146 A CN 201610920146A CN 107974282 A CN107974282 A CN 107974282A
Authority
CN
China
Prior art keywords
catalyst
catalytic cracking
reactor
reaction
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201610920146.7A
Other languages
Chinese (zh)
Other versions
CN107974282B (en
Inventor
谢朝钢
魏晓丽
陈学峰
张久顺
罗斌
罗一斌
田辉平
张执刚
刘银亮
李福超
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Original Assignee
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to CN201610920146.7A priority Critical patent/CN107974282B/en
Publication of CN107974282A publication Critical patent/CN107974282A/en
Application granted granted Critical
Publication of CN107974282B publication Critical patent/CN107974282B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/80—Mixtures of different zeolites
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/06—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/08—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule
    • C07C4/12—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule from hydrocarbons containing a six-membered aromatic ring, e.g. propyltoluene to vinyltoluene
    • C07C4/14—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule from hydrocarbons containing a six-membered aromatic ring, e.g. propyltoluene to vinyltoluene splitting taking place at an aromatic-aliphatic bond
    • C07C4/18—Catalytic processes
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/106—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/7215—Zeolite Beta
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • 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
    • C10G2400/02—Gasoline
    • 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
    • C10G2400/04—Diesel oil
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

It is a kind of to produce low-carbon alkene and the catalytic cracking method of light aromatic hydrocarbons, heavy charge is contacted in first reactor with Part I catalytic cracking catalyst to be reacted, lightweight material rich in saturated hydrocarbons and the lightweight material rich in alkene are contacted with Part II catalytic cracking catalyst and reacted in second reactor and the 3rd reactor, all reaction oil gas and reclaimable catalyst carry out gas solid separation, and wherein reaction oil gas is through the further isolated product comprising low-carbon alkene and light aromatic hydrocarbons；Reclaimable catalyst enters coke burning regeneration in catalyst regenerator after stripping, is recycled in regenerated catalyst Returning reactor；The catalytic cracking catalyst includes 5%~65% natural mineral matter by weight percentage, 10%~60% oxide and 24%~75% Y type molecular sieve and BEA structure molecular screens, 0.1%~15% phosphorus additive and 0.1%~10% metallic addition.The method of the present invention has higher low-carbon alkene and light aromatic hydrocarbons yield.

Description

It is a kind of to produce low-carbon alkene and the catalytic cracking method of light aromatic hydrocarbons
Technical field
The present invention relates to a kind of catalysis conversion method there is no hydrocarbon ils in the case of hydrogen, more specifically to one kind Produce low-carbon alkene and the catalytic cracking method of light aromatic hydrocarbons.
Background technology
Low-carbon alkene using ethene, propylene as representative is the most basic raw material of chemical industry, both at home and abroad it is more with natural gas or Light petroleum fraction is raw material, and low-carbon alkene is produced using steam cracking process in Ethylene Complex unit.In addition to ethene is produced, about 70% propylene, 90% butadiene, 30% aromatic hydrocarbons are all from steam cracking by-product.Although steam cracking technology passes through tens The development in year, technology constantly improve, but still with high energy consumption, production cost height, CO2Discharge capacity is big and product structure is not easy to adjust Limit to etc. technology, the technology of traditional steam cracking production ethene and propylene is faced with acid test.
Light aromatic hydrocarbons (benzene, toluene and dimethylbenzene, abbreviation BTX) are also a kind of important Organic Chemicals, yield and scale It is only second to ethene and propylene.Light aromatic hydrocarbons production mostlys come from Reformed Gasoline and cracking of ethylene gasoline.It is expected that future only relies on this A little sources can not meet the market increased requirement of purified petroleum benzin and paraxylene.Using petroleum hydrocarbon catalytic pyrolysis technology, joined by technique The optimization of number and catalyst property, can effectively improve selectivity of light olefin, while voluminous light aromatic hydrocarbons, which is to be currently To following low-carbon alkene and the research hotspot of Aromatics Production Technology.
A kind of method that CN98101765.7 discloses while preparing low-carbon olefins and high aromatic-hydrocarbon gasoline, heavy petroleum hydrocarbon and water The lower part for the compound reactor that steam is formed in riser and dense-phase fluidized bed is contacted with catalyst；Light petroleum hydrocarbon enters compound The top of reactor, that is, dense-phase fluidized bed bottom is contacted with catalyst.This method have the advantage that using identical catalyst and same Reacted in one device, the yield of raising low-carbon alkene particularly propylene, it is left that the arene content in gasoline increases to 80 weight % It is right.
CN200410006189.1 discloses a kind of chemical industry type oil refining method for producing low-carbon alkene and aromatic hydrocarbons, by feedstock oil Or partial hydrogenation recycle oil and regenerated catalytic cracking catalyst, the vapor haptoreaction in catalytic cracking reaction device, obtain Purpose product low-carbon alkene and aromatic hydrocarbons.This method produces the low-carbon alkenes such as propylene, ethene from heavy charge to greatest extent, wherein The yield of propylene % heavy more than 30, while the light aromatic hydrocarbons such as coproduction BTX.CN201010233651.7 discloses a kind of production propylene and light The catalysis conversion method of aromatic hydrocarbons, hydrocarbon raw material are contacted under catalytic cracking condition with catalytic cracking catalyst in compound reactor Reaction, obtains low-carbon alkene, includes carrying rich in the products such as light aromatic hydrocarbons gasoline, further isolated light aromatic hydrocarbons, compound reactor Riser reactors and fluidized-bed reactor.CN103785460A proposes a kind of catalyst for producing low-carbon alkene and its preparation side Method, the catalyst system compounded using the beta-molecular sieve of MFI structure molecular sieve and P Modification, for naphtha catalytic cracking system third Alkene has the productivity of low carbon olefin hydrocarbon of higher.
In conclusion the prior art is using low-carbon alkene as main target yield, coproduction light aromatic hydrocarbons, therefore the production of light aromatic hydrocarbons Rate increases limited, it is necessary on the basis of present technology and catalysis material, exploitation is a kind of have compared with height carbon olefin and The catalytic cracking method of light aromatic hydrocarbons yield.
The content of the invention
The purpose of the present invention is on the basis of existing technology, there is provided a kind of raising low-carbon alkene and light aromatic hydrocarbons yield are urged Change cleavage method.
The method of the present invention includes：
(1), heavy charge is contacted with Part I catalytic cracking catalyst in first reactor and reacted, and obtains first Partial reaction oil gas and reclaimable catalyst；
(2), the lightweight material rich in saturated hydrocarbons and the lightweight material rich in alkene are in second reactor and the 3rd reactor Contact and reacted with Part II catalytic cracking catalyst, obtain Part II reaction oil gas and reclaimable catalyst；
(3), step (1) the Part I reaction oil gas and reclaimable catalyst, step (2) the Part II reaction oil Gas and reclaimable catalyst carry out gas solid separation, and wherein reaction oil gas includes low-carbon alkene and light aromatic hydrocarbons through further isolated Product；Reclaimable catalyst enters coke burning regeneration in catalyst regenerator after stripping, and the regenerated catalyst of activity recovery returns Recycled in reactor；The catalytic cracking catalyst includes following components by weight percentage：
A) 5%~65% natural mineral matter,
B) 10%~60% oxide,
C) 24%~75% Y type molecular sieve and BEA structure molecular screens,
D) with P2O5The phosphorus additive of meter 0.1%~15%, and
E) in terms of oxide 0.1%~10% metallic addition.
The catalytic cracking catalyst that the method for the present invention uses has abundant meso-hole structure and suitable mesoporous acidity, tool There is higher hydrothermal stability, reacted for heavy oil catalytic pyrolysis, conversion ratio is higher, the high income of propylene, BTX high incomes, especially It is that the selectivity of propylene is good.
Method provided by the invention so that petroleum chemical enterprise can use catalysis processing method to substitute hot-working method from oil Distillate produces industrial chemicals to greatest extent, petroleum chemical enterprise is successfully realized that low-carbon makes the transition, alleviates the huge pressure of carbon emission Power, had not only solved the problems, such as that petrochemical material was short, but also improved the economic benefit and social benefit of petrochemical industry.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Attached drawing is for providing a further understanding of the present invention, and a 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 production low-carbon alkene of preferred embodiment and the catalytic pyrolysis side of light aromatic hydrocarbons according to the present invention The flow diagram of method.
Description of reference numerals：
1- first reactors；2- second reactors；The 3rd reactors of 3-；4- settlers；5- regenerators；
6- stripping sections；7- reactor cyclones；8- collection chambers；
9th, 11- reclaimable catalysts inclined tube pipeline；10th, 12- guiding valves to be generated；
13rd, 15- regenerated catalysts inclined tube pipeline；14th, 16- regenerates guiding valve；
17- is the pipeline of second reactor 2 (riser reactor) transferring raw material；
18- is the pipeline of the 3rd reactor 3 (fluidized-bed reactor) transferring raw material；
19- is the pipeline that stripping section 6 conveys steam；
20- main oil gas pipings；
21- is the pipeline of first reactor 1 (riser reactor) transferring raw material；
The pipeline of the main wind entrances of 22-；
23- regenerator cyclone separators；
24- flues.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
Method provided by the invention is so embodied：
This method includes：
(1), heavy charge is contacted with Part I catalytic cracking catalyst in first reactor and reacted, and obtains first Partial reaction oil gas and reclaimable catalyst；
(2), the lightweight material rich in saturated hydrocarbons and the lightweight material rich in alkene are in second reactor and the 3rd reactor Contact and reacted with Part II catalytic cracking catalyst, obtain Part II reaction oil gas and reclaimable catalyst；
(3), step (1) the Part I reaction oil gas and reclaimable catalyst, step (2) the Part II reaction oil Gas and reclaimable catalyst carry out gas solid separation, the reaction oil gas ejector isolated, further isolated ethene, third Alkene, C4 hydrocarbon-fractions and the drippolene rich in light aromatic hydrocarbons；After stripping, a portion is to be generated to urge the reclaimable catalyst isolated Agent uses after being mixed into first reactor with partial regeneration catalyst, and another part reclaimable catalyst enters regenerator, warp It is divided into two parts after regeneration activity recovery back to recycling in first reactor and second reactor.
The catalytic cracking catalyst includes following components by weight percentage：
A) 5%~65% natural mineral matter,
B) 10%~60% oxide,
C) 24%~75% Y type molecular sieve and BEA structure molecular screens,
D) with P2O5The phosphorus additive of meter 0.1%~15%, and
E) in terms of oxide 0.1%~10% metallic addition.
The heavy charge is one kind in petroleum hydrocarbon, mineral oil, artificial oil, animal fat and vegetable fat Or more than one mixture, petroleum hydrocarbon is known to those skilled in the art, for example, it may be decompressed wax oil, normal pressure slag The hydrocarbon ils that oil, decompressed wax oil blending part reduced pressure residual oil or other secondary operation obtain.The hydrocarbon that other secondary operation obtain Oil such as wax tailings, deasphalted oil, furfural treatment raffinate oil in one or more.Mineral oil is selected from liquefied coal coil, tar sand oil With one or more kinds of mixtures in shale oil.Artificial oil evaporates for coal, natural gas or pitch by what F-T was synthesized Divide oil.Saturated hydrocarbon content is 80-95 weight % in heavy charge.
The one kind of the lightweight material rich in saturated hydrocarbons in straight-run naphtha, hydrogasoline and Aromatic raffinate Or it is a variety of, wherein saturated hydrocarbon content is 60-95 weight %.
The lightweight material rich in alkene is selected from C 4 fraction, FCC light petrols, is hydrocracked light naphthar and cracks light vapour One or more in oil, wherein olefin(e) centent are 60-95 weight %.
Catalytic cracking method provided by the invention, using a kind of combined reactor, first is anti-in the compound reactor It is riser reactor to answer device and second reactor；3rd reactor is fluidized-bed reactor.
Catalytic cracking method according to the present invention, the first reactor are heavy charge catalytic cracking reaction devices, institute The condition for the first reactor stated includes：580-650 DEG C of reaction temperature, oil ratio 4-30, absolute reaction pressure (absolute pressure) are 0.15-0.30MPa, reaction time are 0.1-5 seconds.In order to reduce the partial pressure of hydrocarbon feed, diluent is injected into reactor, wherein The diluent is selected from the one or more in vapor, low-carbon alkanes (C1~C4) and nitrogen, and preferable diluent steams for water Gas, the weight ratio of the vapor and hydrocarbon feed is 0.05-0.8:1.
Catalytic cracking method according to the present invention, the second reactor are that the lightweight material catalysis rich in saturated hydrocarbons is split Reactor is solved, the condition of the second reactor includes：600-750 DEG C of the reaction temperature of second reactor, absolute pressure 0.15- 0.30MPa, oil ratio 15-50, reaction time are 0.1-4 seconds.
Catalytic cracking method according to the present invention, the 3rd reactor are the lightweight material catalytic pyrolysis rich in alkene Reactor, the condition of the 3rd reactor include：Reaction temperature is 600-750 DEG C, and absolute pressure 0.15-0.30MPa, weighs space-time Speed is 0.2-30h-1。
Catalytic cracking method according to the present invention, the Part I catalytic cracking catalyst are reclaimable catalysts and again The mixture of raw catalyst, wherein reclaimable catalyst account for the 5-50 weight % of Part I catalytic cracking catalyst total amount.It is described Part II catalytic cracking catalyst be regenerated catalyst.
Catalytic cracking method provided by the invention, can be same anti-by all feedstock oils introducings in a feed entrance point Answer in device, or the feedstock oil is introduced into same reaction according to identical or different ratio at least two different feed entrance points In device.
Catalytic cracking method according to the present invention, preferably method of the invention further include：Divide from the mixture after contact Separate out reclaimable catalyst, methane, ethene, propylene, mixing C4 components.
Catalytic cracking method according to the present invention, generally to be generated is urged reclaimable catalyst and reaction oil gas are isolated first Agent and reaction oil gas, then by obtained reaction oil gas through follow-up piece-rate system (such as cyclone separator) separation dry gas, The cuts such as liquefied gas, the drippolene rich in light aromatic hydrocarbons, pyrolysis gas oil, then by dry gas and liquefied gas through gas separation equipment into The isolated methane of one step, ethene, propylene, C2-C3 alkane, mixed C4 hydrocarbon class component etc., separate ethene, third from reaction product The methods of alkene, is similar to this area convenient technical process, and the present invention is not limited in this respect, and this is not described in detail here.
Catalytic cracking method according to the present invention, preferably method of the invention further include：Isolated C4 components are returned Go back to second reactor top or the 3rd reactor is contacted as C4 component raw materials with catalytic cracking catalyst.
In catalysis conversion method provided by the invention, the gasoline fraction rich in light aromatic hydrocarbons is after hydrofinishing, by molten Agent extracts to obtain the light aromatic hydrocarbons product such as benzene,toluene,xylene.The gasoline selective hydrofinishing, extracting can use ability The prior art known to field technique personnel.
Catalytic cracking method according to the present invention, preferably method of the invention, which further include, to regenerate obtained regenerated catalyst Stripped and (generally stripped with vapor) in degassing tank and slough the impurity such as gas.
Catalytic cracking method according to the present invention, in regenerative process, generally introduces oxygen-containing gas from the bottom of regenerator, contains Carrier of oxygen for example can be that reclaimable catalyst contacts coke burning regeneration, catalyst coke burning regeneration with oxygen after air introduces regenerator The flue gas generated afterwards enters subsequent power recovery system in regenerator top gas solid separation, flue gas.
Catalytic cracking method according to the present invention, the regenerated operating condition of reclaimable catalyst are preferably：Temperature is 550-750 DEG C, more preferably 600-730 DEG C, more preferably 650-700 DEG C；Gas superficial linear speed is 0.5-3 meter per seconds, excellent Elect 0.8-2.5 meter per seconds, more preferably 1-2 meter per seconds as, reclaimable catalyst mean residence time is 0.6-3 minutes, preferably 0.8- 2.5 minutes, more preferably 1-2 minutes.
Natural mineral matter is selected from kaolin, halloysite, montmorillonite, diatomite, convex in the catalytic cracking catalyst One or more in recessed rod stone, sepiolite, galapectite, hydrotalcite, bentonite and rectorite, natural mineral matter is in terms of butt Content be the weight % of 5 weight %~65, the weight % of preferably 15 weight %~60；The oxide for silica, aluminium oxide, One or more in zirconium oxide, titanium oxide, amorphous silica-alumina, on the basis of catalyst total amount, with weight percent oxide Meter, the content of oxide are the weight % of 10 weight %~60, the weight % of preferably 10 weight %~30, more preferably 12 weight %~28 Weight %.
Y type molecular sieve and the BEA structure molecular screen, on the basis of catalyst total amount, its content is 24 weight %~75 Weight %, the Y type molecular sieve for selected from DASY molecular sieves, containing rare earth DASY molecular sieves, USY molecular sieve, containing rare earth At least one of USY molecular sieve, REY molecular sieves, REHY molecular sieves, HY molecular sieves.
The BEA structure molecular screens are preferably Beta molecular sieves.
The Y type molecular sieve and phosphorous and BEA containing carried metal structure molecular screens weight ratio are 1:8~4:0.1, preferably 0.3:1~20:1.
With P2O5Count and on the basis of catalyst weight, the phosphorus additive content is 0.1-15 weight %, preferably 0.5- 6.5 weight %.
Counted by oxide and on the basis of catalyst weight, the metallic addition content is the weight of 0.1 weight %~10 Measure %, -3.5 weight % of preferably 0.5 weight.The metal be in iron, cobalt, nickel, copper, manganese, zinc, tin, bismuth and gallium at least It is a kind of.
The mesoporous Bronsted acid amount of the catalytic cracking catalyst account for total acid content ratio be 20%~70%, preferably 25%~ 50%.
Total specific surface area of the catalytic cracking catalyst is 240-350m2/g。
The mesopore volume of the catalytic cracking catalyst is 0.14~0.35mL/g, preferably 0.14~0.30mL/g；It is mesoporous Volume and the ratio of total pore volume are 35%~60%.The mesoporous hole for referring to that bore dia is 2~100nm.
Mesoporous pore volume, the total pore volume of the catalytic cracking catalyst are carried out using N2 adsorption BET specific surface area method Measurement；Total specific surface area of the catalyst is measured using N2 adsorption BET specific surface area method；The catalyst it is mesoporous Bronsted acid refers to that kinetic diameter isThe Bronsted acid that can touch of 2,6 di tert butyl pyridine molecule.Mesoporous proton Acid amount is adsorbed infrared acid process using 2,6 di tert butyl pyridine and is measured；Total acid content uses NH3- TPD methods are surveyed Amount.
The preparation method of the catalytic cracking catalyst of the present invention, which includes preparing, includes Y type molecular sieve, aperture is less than's Molecular sieve, natural mineral matter, the microspheroidal composition of adhesive oxides, the present invention are known as first chamber microballoon, by described in The microsphere modified processing of first chamber；The microsphere modified processing of the first chamber is included the following steps：
A, first chamber microballoon is put into alkaline solution and is handled, filtered and wash, obtain first group of alkali process Compound microballoon；
B, the alkali process first chamber microballoon obtained by step a is answered what is be made of fluosilicic acid, organic acid and inorganic acid Closing and handled in acid solution, filter and wash, optional ammonium, which exchanges, washes sodium processing, optionally filtering and optionally washing, optionally drying, Obtain being rich in mesoporous composition microballoon.
C, phosphorus additive and metallic addition are introduced in rich in mesoporous composition microballoon；
D, when calcination process at least 0.5 is small at 400~800 DEG C.
In catalytic cracking catalyst preparation method provided by the invention, the alkaline solution described in step a includes alkalization Compound, it is preferred that the alkali compounds is strong basicity inorganic compound, for example, the alkali compounds is sodium hydroxide, hydrogen One or more in potassium oxide, lithium hydroxide, ammonium hydroxide, high alkali deflection aluminium acid sodium.Alkalescence used in described step a Solution is selected from sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide are molten, in Ammonia, high alkali deflection aluminium acid sodium solution At least one.The alkaline solution is the aqueous solution of alkali compounds.
The catalytic cracking catalyst preparation method provided according to the present invention, a kind of embodiment, alkalescence used in step a Solution preferably includes high alkali deflection aluminium acid sodium, is preferably high alkali deflection aluminium acid sodium solution.Preferably, the high alkali deflection aluminium acid sodium solution In, Na2O content is 270~310g/L, Al2O3Content is 30~50g/L, and solution density is 1.25~1.45g/mL.
The catalytic cracking catalyst preparation method provided according to the present invention, is handled described in step a：Including first is combined Thing microballoon is contacted with alkaline solution, wherein the alkaline solution includes alkali compounds, with the first combination of dry basis Thing microballoon with (ammonium hydroxide is with NH in terms of alkali metal oxide3Meter) alkali compounds weight ratio be 1:(0.01~ 0.35).Preferably, by the first chamber microballoon of dry basis and in terms of alkali metal oxide, (ammonium hydroxide is with NH3Meter) Alkali compounds weight ratio be 1：(0.05~0.25), preferably 1：(0.01~0.15).
Catalytic cracking catalyst preparation method provided by the invention, in being handled described in step a：With the of dry basis The weight ratio of one composition microballoon and water is 1：(5-20).
Catalytic cracking catalyst preparation method provided by the invention, in being handled described in step a：The temperature of the processing is 25~100 DEG C, preferably 40~75 DEG C, more preferably 45~65 DEG C, it is excellent when processing time is that for example, 0.2-6 was small in more than 10 minutes When selecting 0.2-4 small, more preferably 0.3~3 it is small when.
In catalytic cracking catalyst preparation method provided by the invention, in step b, by the alkali process the of gained in step a One composition microballoon is handled in the solution for the Compound-acid being made of fluosilicic acid, organic acid and inorganic acid, and the processing is The alkali process first chamber microballoon is contacted with the compound aqueous acid formed containing fluosilicic acid, organic acid and inorganic acid, Time of contact is, for example, more than 10 minutes, when being, for example, 0.2~10 small or when 0.5~6 is small, filtering, and optionally washing.It is obtained by filtration Filter cake or washing after filter cake, can also be contacted with ammonium salt solution, carry out ammonium exchange washes sodium processing so that obtained catalysis Sodium oxide molybdena is preferably more than 0.15 weight % no more than 0.2 weight % in agent.The ammonium salt can be common ammonium salt, example Such as, selected from least one of ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium hydrogen carbonate, ammonium acetate and ammonium nitrate.
In step b, the temperature of the processing is 25~100 DEG C, preferably 30~75 DEG C, more preferably 45~65 DEG C.
Catalytic cracking catalyst preparation method according to the present invention, wherein, organic acid may be selected from ethylenediamine described in step b At least one of tetraacethyl, oxalic acid, acetic acid, citric acid and sulfosalicylic acid, are preferably oxalic acid, and the inorganic acid may be selected from salt At least one of acid, sulfuric acid and nitric acid, are preferably hydrochloric acid.Preferably, organic acid described in step b is oxalic acid, described inorganic Acid is hydrochloric acid.
In catalytic cracking catalyst preparation method provided by the invention, the condition handled described in step b is：With dry basis The first chamber microballoon of gauge, fluosilicic acid, the weight ratio of inorganic acid and organic acid are 1:(0.003~0.3):(0.01~ 0.45):(0.01~0.55).
Preferably, in catalytic cracking catalyst preparation method provided by the invention, the condition handled described in step b is： Using the weight ratio of the first chamber microballoon of dry basis, fluosilicic acid, organic acid and inorganic acid as 1:(0.005~0.3): (0.02~0.3):(0.02~0.3).The weight ratio of fluosilicic acid and first chamber microballoon is preferably (0.005~0.3)：1；Have The weight ratio of machine acid and first chamber microballoon is preferably (0.02~0.3)：1；The weight of inorganic acid and first chamber microballoon Than being preferably (0.01~0.2)：1.
In catalytic cracking catalyst preparation method provided by the invention, in step b, water and described first in terms of butt The weight ratio of composition microballoon is 3~20：1, preferably 4~15：1, more preferably 5~10：1.
Catalytic cracking catalyst preparation method according to the present invention, wherein, sodium exchange process is washed in ammonium exchange described in step b makes Being contacted with ammonium salt solution with the composition obtained by compound acid treatment, the ammonium salt can be common ammonium salt, For example, selected from least one of ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium hydrogen carbonate, sodium acetate and ammonium nitrate.Ammonium salt is exchanged and washed Filtered after sodium processing, optionally washing, sodium is washed to wash away such as ammonium exchange of the ammonium salt for exchanging sodium and not exchanging in catalyst In, the weight ratio of ammonium salt solution and the composition obtained by compound acid treatment is 5~20：1, the concentration of ammonium salt solution For 1~10 weight %, Contact Temperature is 30~80 DEG C, when time of contact is 0.5~2 small..
In catalytic cracking catalyst preparation method provided by the invention, the washing described in step b is conventional method, such as It is 1 according to first chamber microballoon and water weight ratio：5~10 weight ratio is eluted with water.The usual washing, makes washing Cleaning solution afterwards is neutrality, such as pH value is 6~8.
Phosphorus additive and metal addition are introduced in catalytic cracking catalyst preparation method provided by the invention, described in step c Agent is contacted including will be enriched in mesoporous composition microballoon with phosphorus-containing compound and metallic compound.It is described to will be enriched in mesoporous combination Thing microballoon is contacted with phosphorus-containing compound and metallic compound, can will be enriched in mesoporous composition microballoon and phosphorus-containing compound and gold Belong to compound contact at the same time, can also be contacted respectively with phosphorus-containing compound and metallic compound, or part phosphorus-containing compound and Metallic compound contacts at the same time with rich in mesoporous composition microballoon, part phosphorus-containing compound and metallic compound by respectively with Rich in mesoporous composition micro-sphere contacts.By carrying out the contact, to be impregnated and/or ion exchange is drawn in the catalyst Enter phosphorus additive and metallic addition.The order for introducing phosphorus additive and metallic addition does not have particular/special requirement, such as can be first Phosphorus additive is introduced, metallic addition is re-introduced into, can also first introduce metallic addition and be re-introduced into phosphorus additive or introduce at the same time Phosphorus additive and metallic addition.When priority introduces phosphorus additive and metallic addition, the combination after a kind of additive is introduced Other additive can be dried and/or be re-introduced into after roasting to thing, and dry and roasting method is existing method, for example, can be with When roasting 0.5~8 is small at 350~650 DEG C.Each additive can be incorporated into by one or many contact with composition It is described to be rich in mesoporous composition microballoon.
In catalytic cracking catalyst preparation method provided by the invention, the method for phosphorus additive is introduced described in step c to be included With phosphorus-containing compound to being impregnated rich in mesoporous composition microballoon and/or ion exchange.The phosphorus-containing compound may be selected from One or more in phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate.
In the catalytic cracking catalyst preparation method of the present invention, the method for metallic addition is introduced described in step c to be included using Metallic compound rich in mesoporous composition microballoon to being impregnated and/or ion exchange.Wherein, described metallic compound choosing One or more from the compound of Fe, Co, Ni, Cu, Mn, Zn, Sn, Bi and Ga.Described metallic compound is metal Water soluble salt, the water soluble salt of described metal are selected from one kind in the sulfate of metal, nitrate or chlorate.
Catalytic cracking catalyst preparation method according to the present invention, the condition of calcination process includes described in step d：At roasting The atmosphere of reason is air atmosphere, nitrogen atmosphere or steam atmosphere or the mixture atmosphere of above-mentioned atmosphere；Calcination temperature is 400- 800 DEG C, when roasting time is 0.5-8 small.Preferably, when calcination process 0.5~8 is small at 500~600 DEG C.
The method according to the invention, the calcination process process described in step d can be wet roastings, described wet roasting be 1~ Under 100 volume % vapor (the vapor % i.e. containing 1~100 volume in atmosphere), more preferably 100% steam atmosphere into OK.
A kind of embodiment according to the present invention, when the method for the present invention carries out in riser reactor, is generally pressed Following steps carry out：
Regenerated catalyst (catalytic cracking catalyst) enters the pre lift zone of riser reactor, in the work of pre-lift medium Flowed up under, the injecting lift pipe reactor lower part together with atomizing steam of the feedstock oil after preheating, connects with regenerated catalyst Progress catalytic cracking reaction is touched to flow up at the same time；Reaction oil gas and the boosted pipe reactor outlet of reclaimable catalyst enter fluidisation Bed reactor, reaction oil gas secondary response again, after reaction the boosted pipe reactor outlet of logistics enter in cyclone separator, isolate Reaction oil gas ejector, further isolated methane, ethene, propylene, C4 hydrocarbon, drippolene rich in light aromatic hydrocarbons etc. evaporate Point；The reclaimable catalyst isolated enters coke burning regeneration in regenerator, and the regenerated catalyst of activity recovery returns to lifting tube reaction Recycled in device.
The embodiment of the present invention is described in detail below in conjunction with attached drawing.It should be appreciated that this place is retouched The embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
Fig. 1 is the flow diagram of production low-carbon alkene provided by the invention and the catalytic cracking method of light aromatic hydrocarbons.
The technological process of method provided by the invention is illustrated referring to Fig. 1：Shown in Fig. 1, from pipeline 13 again Raw catalyst enters the bottom of first reactor 1 after regeneration guiding valve 14 is adjusted, and the reclaimable catalyst from pipeline 11 is through to be generated Guiding valve 12 enters the bottom of first reactor 1 after adjusting, the two mixture moves upwards along riser, and feedstock oil is through 21 note of pipeline Enter the bottom of first reactor 1, catalytic cracking reaction occurs on mixed catalyst for feedstock oil, after reaction logistics enter settler Cyclone separator 7 in 4, realizes the separation of reclaimable catalyst and reaction product oil gas, and reaction product oil gas enters collection chamber 8, Regenerated catalyst from pipeline 15 enters the bottom of second reactor 2, the lightweight of enriched saturated hydrocarbon after regeneration guiding valve 16 is adjusted Bottom of the feedstock oil through 17 injected in second reactor 2 of pipeline, feedstock oil heat catalyst on occur catalytic cracking reaction and to Upper movement, lower part of the lightweight material oil of rich olefins through 17 injected in second reactor 2 of pipeline, with the existing logistics of second reactor Mixing, into fluidized-bed reactor 3, occurs catalytic cracking reaction, after reaction logistics enter the cyclone separator 7 in settler 4, Realize the separation of reclaimable catalyst and reaction product oil gas, reaction product oil gas enters collection chamber 8, and catalyst fines are returned by dipleg Return settler.
Reclaimable catalyst flows to stripping section 6 in settler, is contacted with the steam from pipeline 19.The vapour from reclaimable catalyst The reaction product oil gas of proposition enters collection chamber 8 after cyclone separator.Part reclaimable catalyst after stripping is through guiding valve 9 to be generated After adjusting, through pipeline 10 into regenerator 5, the coke on the air contact burning-off reclaimable catalyst from pipeline 22, makes inactivation Reclaimable catalyst regeneration, upper gas flue 24 of the flue gas through cyclone separator 23 enter subsequent power recovery system； Part reclaimable catalyst after stripping enters 1 bottom cycle of first reactor after guiding valve 11 to be generated adjusting, through pipeline 12 and uses.
The following examples will be further described this method, but not thereby limiting the invention.
Feedstock oil used is vacuum distillate in embodiment 1-2 and comparative example, its property is as shown in table 1.
Catalyst used in comparative example is conventional catalytic pyrolysis special-purpose catalyst, product designation MMC-2.Embodiment institute Catalytic cracking catalyst preparation method is summarized as follows：
By 267g Aluminum sols (Shandong catalyst branch company, alumina content are 22.5 weight %) and 200g kaolin (Soviet Union State China Kaolin Co., Ltd, 75 weight % of solid content) mixing, and it is 28 weight % to be configured to solid content with decationized Y sieve water Slurries, stirring 2 it is small when after add (in terms of butt) 45g USY (asphalt in Shenli Refinery of Sinopec Catalytica Inc., Content of rare earth is with RE2O3It is calculated as 1.5 weight %, silica alumina ratio SiO2/Al2O3Molar ratio is 5.8) and 45g Beta molecular sieves are (Chinese Asphalt in Shenli Refinery of Effect of Catalysis In Petrochemistry agent limited company, silica alumina ratio 30), forming composition slurries, (solid content is 35% weight Amount), stir evenly, composition microballoon is made in spray drying, and said composition microballoon then is made the when 500 DEG C of roastings 2 are small One composition microballoon A1.
Take first chamber microballoon A1 (butt quality) 200g made above, add water be beaten solid content is 10 weight % Slurries, add 15.1g high alkali deflection aluminium acid sodium solution (Na2O is 290g/L, Al2O3For 40g/L, solution density 1.353g/ ML), be warming up to 50 DEG C of constant temperature stirring 0.5h, filtering, wash to it is neutral (wash to neutrality and refer to the cleaning solution after washing as neutrality, PH 6~8)；By filter cake plus water be beaten solid content be 10 weight % slurries, in stirring add 6.2g oxalic acid, then add 54g hydrochloric acid (HCl mass fractions 10%) and 33.4g silicate fluoride solutions (3 weight % of fluosilicic acid concentration), are warming up to 50 DEG C of constant temperature and stir 1h is mixed, filtering, washing to neutrality obtain filter cake；By filter cake plus water be beaten solid content is that 40 weight % are rich in mesoporous combination Thing microballoon slurries, by 12.8g H3PO4(concentration 85%) and 7.2g Cu (NO3)2·3H2O is dissolved in 60g water, and rich in mesoporous Composition microballoon slurries are mixed with dipping, drying；Gained sample when 550 DEG C of calcination process 2 are small, i.e., split by catalysis provided by the invention Solve catalyst A.In terms of catalyst A percentage by weights, the composition of catalyst A is as follows：47.1% natural mineral matter (in terms of butt), 18.8% adhesive oxides (in terms of oxide), molecular sieve 28.3% (in terms of butt), 3.5% phosphorus additive is (with P2O5 Meter) and 2.3% metallic addition (in terms of oxide).The ratio that the mesoporous Bronsted acid amount of catalyst A accounts for total acid content is 50%, Total specific surface area is 278m2The ratio of/g, mesopore volume 0.15mL/g, mesopore volume and total pore volume is 37%.
Specific surface area of the present invention is measured using GBT5816 standard methods.
The pore volume of the present invention is measured using GB/T5816-1995 standard methods.
The total acid content of the present invention uses NH3- TPD methods are measured, referring to the research method of solid catalyst, oil Work, 30 (12), 2001：952.
The mesoporous Bronsted acid of the method for the present invention adsorbs infrared acid process measure using 2,6 di tert butyl pyridine.Specifically Method is：Catalyst is pressed into 10mg/cm2Thin slice, be put into band CaF2In the infrared pond of window.First vacuumized at 400 DEG C, then Drop to 150 DEG C of absorption 2,6- di-tert-butyl pyridines 15 minutes, then vacuumize 1 it is small when.Room temperature collection spectrogram is dropped to, and calculates matter Sub- acid amount.Referring to Applied Catalysis A:General, 294,2005：92.
The P of the present invention2O5, metallic addition content is measured using GB/T 30905-2014 standard methods.
RIPP standard methods of the present invention for details, reference can be made to《Petrochemical Engineering Analysis method》, Yang Cui surely compile by grade, and 1990 Year version.
Comparative example
Tested according to the flow of Fig. 1, feedstock oil is vacuum distillate, using MMC-2 catalyst, on middle- scale device Tested, three equal atmospheric operations of reactor, hydrocracking tail oil enters riser 1, in 580 DEG C of reaction temperature, reaction Between 2.0 seconds, regenerated catalyst and the weight ratio 10 of reclaimable catalyst mixture and feedstock oil, the weight ratio of vapor and feedstock oil Enter whirlwind from reactor outlet to carry out cracking reaction, reaction oil gas and vapor and reclaimable catalyst under conditions of 0.25 Separator.
Aromatic raffinate enters 2 bottom of riser, in 625 DEG C of reaction temperature, 1.8 seconds reaction time, regenerated catalyst with The weight ratio of the weight ratio 15 of feedstock oil, vapor and feedstock oil carries out cracking reaction under conditions of being 0.25, reaction oil gas and Vapor and reclaimable catalyst enter fluidized-bed reactor from reactor outlet, in 610 DEG C of reaction temperature, weight (hourly) space velocity (WHSV) 3.0h-1Second under the conditions of the reaction was continued, after reaction logistics enter closed cyclone separator, reaction oil gas and reclaimable catalyst quickly divide From reaction oil gas is cut in piece-rate system by boiling range, so as to obtain methane, ethene, propylene, mixing four component of carbon and be rich in The cuts such as the drippolene of light aromatic hydrocarbons；Reclaimable catalyst enters stripping section under the effect of gravity, and to be generated urge is stripped off by vapor The hydrocarbon product adsorbed in agent, the part reclaimable catalyst after stripping, which connects, enters regenerator, is regenerated with air contact, Enter back into riser reactor 2 to recycle, or part reclaimable catalyst is recycled into riser reactor 1；Operate bar Part and product distribution are listed in table 2.
From the results shown in Table 2, ethylene yield is 8.2 weight %, and productivity of propylene is 22.3 weight %, light aromatic hydrocarbons (BTX) yield is 8.7 heavy %, and the research octane number (RON) of gasoline is 93.
Embodiment
Tested according to the flow of Fig. 1, feedstock oil is vacuum distillate, using MMC-2 catalyst, on middle- scale device Tested, three equal atmospheric operations of reactor, hydrocracking tail oil enters riser 1, in 580 DEG C of reaction temperature, reaction Between 2.0 seconds, regenerated catalyst and reclaimable catalyst mixture (wherein reclaimable catalyst accounts for 20 weight % of catalyst mixture) with The weight ratio of the weight ratio 10 of feedstock oil, vapor and feedstock oil carries out cracking reaction under conditions of being 0.25, reaction oil gas and Vapor and reclaimable catalyst enter cyclone separator from reactor outlet.
Aromatic raffinate (saturated hydrocarbon content is 87 weight %) enters 2 bottom of riser, in 625 DEG C of reaction temperature, reaction The weight ratio of the weight ratio 15 of 1.8 seconds time, regenerated catalyst and feedstock oil, vapor and feedstock oil be 0.25 under conditions of into Row cracking reaction, reaction oil gas and vapor and reclaimable catalyst, (olefin(e) centent is 70 weights to the petroleum benzin rich in alkene Amount %) exported from riser 2 into fluidized bed 3, in 610 DEG C of reaction temperature, weight (hourly) space velocity (WHSV) 3.0h-1The reaction was continued under the conditions of second, Logistics enters closed cyclone separator after reaction, and reaction oil gas and reclaimable catalyst quick separating, reaction oil gas are pressed in piece-rate system Boiling range is cut, so as to obtain methane, ethene, propylene, the mixing cut such as four component of carbon and the drippolene rich in light aromatic hydrocarbons； Reclaimable catalyst enters stripping section under the effect of gravity, and the hydrocarbon product adsorbed on reclaimable catalyst, vapour are stripped off by vapor Part reclaimable catalyst after carrying, which connects, enters regenerator, is regenerated with air contact, enters back into riser reactor 2 and circulates Use, or part reclaimable catalyst is recycled into riser reactor 1；Operating condition and product distribution are listed in table 2.
From table 2 it can be seen that ethylene yield is 13.2 weight %, productivity of propylene is 33.4 weight %, and light aromatic hydrocarbons yield is 14.1 heavy %, meanwhile, the gasoline with higher octane can be obtained, the research octane number (RON) of gasoline is 98.5.
Table 1
Density (20 DEG C)/gcm-3 0.8881
Refraction index/70 DEG C 1.4784
Condensation point/DEG C >50
Aniline point/DEG C 112.9
Carbon residue/% 2.7
Four components/%
Saturated hydrocarbons 62.1
Aromatic hydrocarbons 25.2
Colloid 12.6
Asphalitine 0.1
Boiling range/DEG C
Initial boiling point 339
5% 388
10% 421
30% 473
50% 526
70% -
Tenor/μ gg-1
Fe 2.3
Ni 3.0
Cu <0.1
V 0.1
Na 2.6
Table 2
Comparative example Embodiment
First reactor condition
Reaction temperature, DEG C 580 580
Reaction time, second 2 2
Oil ratio 10 10
The weight ratio of vapor/raw material 0.25 0.25
Second reactor condition
Reaction temperature, DEG C 625 625
Reaction time, second 1.8 1.8
Oil ratio 15 15
The weight ratio of vapor/raw material 0.25 0.25
3rd reactor condition
Reaction temperature, DEG C 610 610
Weight (hourly) space velocity (WHSV), h-1 3.0 3.0
Product is distributed, weight %
H2+CH4+C2H6 10.2 7.2
Wherein ethene 8.2 13.2
Liquefied gas 41.3 51.3
Wherein propylene 22.3 33.4
Wherein C4 components 15.5 14.6
Gasoline 27.9 18.9
Wherein BTX 8.7 14.1
Diesel oil 3 2
Coke 9.4 7.4
It is total 100.0 100.0
Gasoline Research octane number 93 98.5
The method of the present invention has the gross production rate height of ethene, propylene and light aromatic hydrocarbons it can be seen from the result of embodiment.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance In the case of shield, it can be combined by any suitable means.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should equally be considered as content disclosed in this invention.

Claims (25)

1. a kind of produce low-carbon alkene and the catalytic cracking method of light aromatic hydrocarbons, it is characterised in that this method includes：
(1), heavy charge is contacted with Part I catalytic cracking catalyst in first reactor and reacted, and obtains Part I Reaction oil gas and reclaimable catalyst；
(2), the lightweight material rich in saturated hydrocarbons and the lightweight material rich in alkene are in second reactor and the 3rd reactor and The contact of two partially catalyzed catalyst for cracking is reacted, and obtains Part II reaction oil gas and reclaimable catalyst；
(3), step (1) the Part I reaction oil gas and reclaimable catalyst, step (2) the Part II reaction oil gas and Reclaimable catalyst carries out gas solid separation, and wherein reaction oil gas is through the further isolated production comprising low-carbon alkene and light aromatic hydrocarbons Thing；Reclaimable catalyst enters coke burning regeneration in catalyst regenerator after stripping, and the regenerated catalyst of activity recovery returns to reaction Recycled in device；The catalytic cracking catalyst includes following components by weight percentage：
A) 5%~65% natural mineral matter,
B) 10%~60% oxide,
C) 24%~75% Y type molecular sieve and BEA structure molecular screens,
D) with P2O5The phosphorus additive of meter 0.1%~15%, and
E) in terms of oxide 0.1%~10% metallic addition.
2. according to the method described in claim 1, it is characterized in that the heavy charge be selected from petroleum hydrocarbon, mineral oil, One or more kinds of mixtures in artificial oil, animal fat and vegetable fat.
3. according to the method described in claim 2, it is characterized in that the saturated hydrocarbon content of the heavy charge is 80-95 weights Measure %.
4. according to the method described in claim 1, it is characterized in that the lightweight material rich in saturated hydrocarbons is selected from straight run stone One or more in cerebrol, hydrogasoline and Aromatic raffinate.
5. the according to the method described in claim 4, it is characterized in that saturated hydrocarbon content of the lightweight material rich in saturated hydrocarbons For 60-95 weight %.
6. according to the method described in claim 1, it is characterized in that the lightweight material rich in alkene is selected from C 4 fraction, FCC Light petrol, the one or more being hydrocracked in light naphthar and pyrolysis gasoline.
7. according to the method described in claim 6, it is characterized in that the olefin(e) centent of the lightweight material rich in alkene is 60- 95 weight %.
8. according to the method described in claim 1, it is characterized in that the first reactor is riser, second reactor is to carry Riser, the 3rd reactor are fluid bed.
9. according to the method described in claim 1, it is characterized in that 580-650 DEG C of the reaction temperature of the first reactor, Oil ratio is 4-30, and the reaction time is 0.1-5 seconds.
10. according to the method described in claim 1, it is characterized in that 600-750 DEG C of the reaction temperature of the second reactor, Oil ratio is 15-50, and the reaction time is 0.1-4 seconds.
11. according to the method described in claim 1, it is characterized in that 600-750 DEG C of the reaction temperature of the 3rd reactor, Weight (hourly) space velocity (WHSV) 0.2-30h-1。
12. the method according to claim 1, it is characterised in that the Part I catalytic cracking catalyst is reclaimable catalyst With the mixture of regenerated catalyst.
13. method according to claim 12, it is characterised in that catalysis to be generated in the Part I catalytic cracking catalyst Agent accounts for the 5-50 weight % of Part I catalytic cracking catalyst total amount.
14. the method according to claim 1, it is characterised in that the natural mineral matter includes kaolin, halloysite, illiteracy One or more in de- soil, diatomite, convex-concave rod stone, sepiolite, galapectite, hydrotalcite, bentonite and rectorite.
15. the method according to claim 1, it is characterised in that the oxide is silica, aluminium oxide, zirconium oxide, oxidation One or more in titanium, amorphous silica-alumina.
16. the method according to claim 1, it is characterised in that the Y type molecular sieve is selected from DASY molecular sieves, containing rare earth In DASY molecular sieves, USY molecular sieve, the USY molecular sieve containing rare earth, REY molecular sieves, REHY molecular sieves, HY molecular sieves at least It is a kind of.
17. the method according to claim 1, it is characterised in that the BEA structure molecular screens are Beta molecular sieves.
18. according to the method in claim 1, it is characterised in that the Y type molecular sieve and BEA structure molecular screen weight ratios be 1:8~4:0.1.
19. the method according to claim 1, it is characterised in that the phosphorus additive content is 0.5-6.5 weights %.
20. the method according to claim 1, it is characterised in that the content of the metallic addition is 0.5-3.5 weight %.
21. the method according to claim 1, its feature is selected from iron, cobalt, nickel, copper, manganese, zinc, tin, bismuth in the carried metal At least one of with gallium.
22. the method according to claim 1, it is characterised in that the mesoporous Bronsted acid amount of catalytic cracking catalyst accounts for total acid content Ratio is 20%~70%.
23. method according to claim 21, it is characterised in that the mesoporous Bronsted acid amount of the catalytic cracking catalyst accounts for total acid The ratio of amount is 25%~50%.
24. the method according to claim 1, it is characterised in that total specific surface area of the catalytic cracking catalyst is 240- 350m2/g。
25. the method according to claim 1, it is characterised in that the mesopore volume of the catalytic cracking catalyst for 0.14~ The ratio of 0.35mL/g, mesopore volume and total pore volume is 35%~60%.
CN201610920146.7A 2016-10-21 2016-10-21 Catalytic cracking method for producing low-carbon olefin and light aromatic hydrocarbon Active CN107974282B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610920146.7A CN107974282B (en) 2016-10-21 2016-10-21 Catalytic cracking method for producing low-carbon olefin and light aromatic hydrocarbon

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610920146.7A CN107974282B (en) 2016-10-21 2016-10-21 Catalytic cracking method for producing low-carbon olefin and light aromatic hydrocarbon

Publications (2)

Publication Number Publication Date
CN107974282A true CN107974282A (en) 2018-05-01
CN107974282B CN107974282B (en) 2020-09-22

Family

ID=62003859

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610920146.7A Active CN107974282B (en) 2016-10-21 2016-10-21 Catalytic cracking method for producing low-carbon olefin and light aromatic hydrocarbon

Country Status (1)

Country Link
CN (1) CN107974282B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111822033A (en) * 2019-04-23 2020-10-27 中国石油化工股份有限公司 Hydrocarbon oil catalytic cracking catalyst rich in naphthenic cyclic hydrocarbon, and preparation method and application method thereof
CN114057533A (en) * 2020-07-31 2022-02-18 中国石油化工股份有限公司 Method for producing light aromatic hydrocarbon and low-carbon olefin

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4740292A (en) * 1985-09-12 1988-04-26 Mobil Oil Corporation Catalytic cracking with a mixture of faujasite-type zeolite and zeolite beta
CN101134172A (en) * 2006-08-31 2008-03-05 中国石油化工股份有限公司 Hydrocarbons conversion catalyzer
CN102337154A (en) * 2010-07-22 2012-02-01 中国石油化工股份有限公司 Method for catalytic conversion production of propylene and light aromatics
CN104549463A (en) * 2013-10-22 2015-04-29 中国石油化工股份有限公司 Cracking catalyst containing metallic oxide modified beta zeolite

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4740292A (en) * 1985-09-12 1988-04-26 Mobil Oil Corporation Catalytic cracking with a mixture of faujasite-type zeolite and zeolite beta
CN101134172A (en) * 2006-08-31 2008-03-05 中国石油化工股份有限公司 Hydrocarbons conversion catalyzer
CN102337154A (en) * 2010-07-22 2012-02-01 中国石油化工股份有限公司 Method for catalytic conversion production of propylene and light aromatics
CN104549463A (en) * 2013-10-22 2015-04-29 中国石油化工股份有限公司 Cracking catalyst containing metallic oxide modified beta zeolite

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111822033A (en) * 2019-04-23 2020-10-27 中国石油化工股份有限公司 Hydrocarbon oil catalytic cracking catalyst rich in naphthenic cyclic hydrocarbon, and preparation method and application method thereof
CN111822033B (en) * 2019-04-23 2023-04-07 中国石油化工股份有限公司 Hydrocarbon oil catalytic cracking catalyst rich in naphthenic cyclic hydrocarbon, and preparation method and application method thereof
CN114057533A (en) * 2020-07-31 2022-02-18 中国石油化工股份有限公司 Method for producing light aromatic hydrocarbon and low-carbon olefin
CN114057533B (en) * 2020-07-31 2023-12-12 中国石油化工股份有限公司 Method for producing light aromatic hydrocarbon and low-carbon olefin

Also Published As

Publication number Publication date
CN107974282B (en) 2020-09-22

Similar Documents

Publication Publication Date Title
US8696887B2 (en) Catalytic conversion process
CN107971010A (en) It is a kind of to produce low-carbon alkene and the catalytic cracking method of light aromatic hydrocarbons
CN103725320B (en) The petroleum hydrocarbon catalytic cracking process of a kind of high output of ethylene and/or propylene and device thereof
CN107974286A (en) It is a kind of to produce low-carbon alkene and the catalytic cracking method of light aromatic hydrocarbons
CN101434862B (en) Method for reducing sulfide in light hydrocarbon oil
CN103059926B (en) Method for producing low carbon olefin by catalytic conversion of lightweight hydrocarbon oil
CN105439798A (en) Method for producing ethylene and propylene by catalytic cracking of lightweight petroleum hydrocarbons
CN108659883B (en) Method and system for gasoline desulfurization and aromatization
CN107974282A (en) It is a kind of to produce low-carbon alkene and the catalytic cracking method of light aromatic hydrocarbons
CN107974281A (en) It is a kind of to produce low-carbon alkene and the catalytic cracking method of light aromatic hydrocarbons
CN107974285A (en) It is a kind of to produce low-carbon alkene and the catalytic cracking method of light aromatic hydrocarbons
GB1570682A (en) Hydrocarbon catalytic cracking process
CN107971012A (en) It is a kind of to produce low-carbon alkene and the catalytic cracking method of light aromatic hydrocarbons
US10907110B2 (en) Process for treating gasoline
CN102031138B (en) Catalytic conversion method for productive diesel and propylene
CN107974297A (en) A kind of vapour oil treatment process
CN107974288A (en) A kind of vapour oil treatment process
CN107974284B (en) Catalytic cracking method for producing low-carbon olefin and light aromatic hydrocarbon
CN103725321B (en) The petroleum hydrocarbon catalytic cracking process of a kind of high output of ethylene and/or propylene and device thereof
CN107974283A (en) It is a kind of to produce low-carbon alkene and the catalytic cracking method of light aromatic hydrocarbons
CN105505454B (en) A kind of shale oil fluidized catalytic cracking method
CN102134509B (en) Catalytic conversion method for preparing propylene and high-octane gasoline with crude oil
CN107974292A (en) A kind of vapour oil treatment process
CN107974293A (en) A kind of processing method and system of gasoline
CN107974296B (en) Gasoline treatment method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant