CN103059925B - Method for producing low carbon olefin by catalytic conversion of lightweight petroleum hydrocarbon - Google Patents
Method for producing low carbon olefin by catalytic conversion of lightweight petroleum hydrocarbon Download PDFInfo
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Abstract
The invention relates to a method for method for producing low carbon olefin by catalytic conversion of lightweight petroleum hydrocarbon, which is characterized in that a lightweight hydrocarbon oil raw material is introduced at the bottom of a riser reactor, and is connected to a regenerated catalyst for a catalytic cracking reaction and simultaneously flows upwardly, the reaction oil gas at an outlet of the riser reactor and a catalyst to be generated enable gas-solid separation after being introduced in a cyclone separator, the separated reaction oil gas is further separated to obtain ethane, propylene, C2-C3 alkane and C4 hydrocarbon fraction and other products; the separated catalyst to be generated is stripped, scorched and regenerated for cycle usage; the riser reactor is arranged in a catalyst reactivator, the outlet of the riser reactor is communicated with the cyclone separator, a gas phase outlet of the cyclone separator is communicated with a subsequent separating system through a collection chamber, and a solid phase outlet of the cyclone separator is communicated with the inner part of the catalyst reactivator through a stripping stage. A settler is arranged at the upper part of the stripping stage. According to the invention, the riser reactor is placed in the catalyst reactivator, the energy is saved, and the thermal balance problem due to insufficient scorching of the lightweight hydrocarbon oil can be simultaneously reduced.
Description
Technical field
The present invention relates to a kind of catalysis conversion method not depositing hydrocarbon ils in the context of hydrogen, more particularly, relate to a kind of method of light hydrocarbon oil producing light olefins through catalytic conversion.
Background technology
Ethene is one of most important basic material of petrochemical industry, by vinyl polymerization, with the alkylation of benzene and the addition reaction with water, oxygen, halogen, a series of extremely valuable derivative can be obtained.World Ethylene Industry continues the situation that remain stable development.At present, the ethene of about 98% comes from tube furnace steam cracking technology in the world, and in ethylene production raw material, petroleum naphtha accounts for 46%, and ethane accounts for 34%.
Propylene is one of most important alkene, and consumption is only second to ethene.The derivative of propylene research on maximum utilized quantity is polypropylene, accounts for 61% of global propylene consumption.2005, about 62% propylene in the whole world was from the coproduction of preparing ethylene by steam cracking, and 34% propylene, from refinery catalytic cracking device by-product, also has 4% propylene from dehydrogenating propane and Ethylene/Butylene metathesis reaction.
At present, steam cracking technology becomes better and approaching perfection day by day, and is the process consuming the energy in a large number, is used again and the limitation of high temperature material, and the potentiality improved further are very little.The output of the ethene that hydrocarbon vapours cracking is produced and propylene is very large, and the raising of small yield and the saving of small raw material and the energy all will bring considerable economic benefit.In order to improve the selectivity of cracking process alkene, reduce scission reaction temperature, the yield of further increase ethene and propylene, by improving the diversity of raw material, develop multiple new ethylene, as preparing low-carbon olefin by catalytically cracking technology, methane oxidation coupling technology, oxidative dehydrogenation of ethane technology, natural gas via methyl alcohol or dimethyl ether alkene technology etc., wherein producing olefin hydrocarbon by catalytic pyrolysis technology is compared with steam cracking technology, have and can reduce cracking temperature, improve ethene and propene yield and scission reaction selectivity, save the advantage of energy, thus become the technology of very attractive.
CN1406253A discloses a kind of method that fluid catalytic cracking process prepares propylene, is incorporated in the process unit be made up of reaction zone, stripping zone, catalyst regeneration zones and fractionation zone by naphtha stream.Make feed naphtha at reaction zone and catalyst exposure, described catalyzer is containing the mean pore size of 10 ~ 50 heavy % that have an appointment lower than the crystalline zeolite of about 0.7nm, and reaction conditions comprises: temperature about 500 ~ 650 DEG C, hydrocarbon partial pressure is 10 ~ 40psia.Top, reaction zone realizes oil gas and catalyst separating, and makes granules of catalyst by stripping zone, then enters catalyst regeneration zones.Use steam stripped volatile matter in stripping zone, granules of catalyst delivers to catalyst regeneration zones, and incinerated by the coke on catalyzer at this, then catalyst recirculation is to reaction zone.The top product obtained from reaction zone is sent to fractionation zone, reclaim C3 product flow, and the logistics of rich C4 and/or C5 alkene is recycled to stripping zone at this.
CN101279881A discloses a kind of method that catalytic pyrolysis petroleum naphtha produces ethene and propylene, this invention is by adopting with the petroleum naphtha of C4 ~ C10 hydrocarbon composition as raw material, after raw material hydrocarbon vaporization, first mix with rare gas element, wherein the mol ratio of rare gas element and petroleum naphtha is greater than 0 ~ 5.0: 1, be 580 ~ 750 DEG C in temperature of reaction, reaction pressure (in gauge pressure) is greater than 0 ~ 0.5MPa, weight space velocity 0.5 ~ 3h
-1under the condition of water/petroleum naphtha weight ratio 0 ~ 5: 1, material mixed gas and catalyst exposure react and generate ethene and propylene, wherein used catalyst is selected from the technical scheme of at least one in ZSM-5/ mercerization zeolite symbiosis molecular screen, ZSM-5/ beta zeolite coexisting molecular sieve or ZSM-5/Y zeolite coexisting molecular sieve, mainly solves the problem that life-span is shorter, palpus consumes a large amount of water vapour that naphtha catalytic pyrolysis preparing ethylene propylene reacting middle catalyst causes because of coking.
CN1958731A discloses a kind of catalytic thermal cracking process to prepare lower olefine method.To the cracking petroleum hydrocarbon raw material of petroleum naphtha, solar oil and hydrogenation tail oil be comprised, and by the beds of connect up and down two filling different catalysts a and b, carry out catalytic cracking reaction, obtain olefine in low carbon number.Preferred employing double-reactor dual catalyst bed technique, by two sections of fixed-bed reactor series connection; Or adopt single reactor dual catalyst bed technique, in same fixed-bed reactor, load two beds.The method of this invention can improve the transformation efficiency of raw material, and improves the selectivity of reaction, increases the yield of object product (ethene and propylene).
CN1566272A discloses a kind of method utilizing light petroleum fraction catalyzed conversion to produce ethene and propylene, is that the light petroleum fraction being rich in alkene is contacted with the five-ring high silica zeolite catalyst of heat and reacted under catalyticing conversioning condition in main reaction region; Reaction product isolated and reclaimable catalyst; Reaction product is separated into further after being drawn by main reaction region and is rich in ethene, below the C4 cut of propylene and C4 and more than C4 cut; Reclaimable catalyst enters revivifier after stripping, coke burning regeneration under oxygen-containing gas exists; The regenerated catalyst of heat is introduced in pre-reaction zone and contacts with above-mentioned C4 and more than the C4 cut from main reaction region, react, and the oil agent mixture generated returns to main reaction region and recycles.
Because the cracking reaction transformation efficiency of Deep Catalytic Cracking process is high, temperature of reaction is high, cracking reaction heat is large, and the heat needed in reaction is more Conventional catalytic cracking or other catalysis conversion method is many, and the coke that self cracking generates often can not meet the thermally equilibrated demand of reaction-regeneration system self.Above-mentioned prior art proposes the method and the catalyzer that by catalytic cracking reaction process, petroleum hydrocarbon raw material are converted into low-carbon alkene, but fails to solve the problem of reaction heat deficiency in light hydrocarbon oil cracking process.
Summary of the invention
The object of this invention is to provide and a kind ofly save energy consumption, light hydrocarbon oil producing light olefins through catalytic conversion that selectivity is good, i.e. the method for ethene and propylene.
The method of light hydrocarbon oil producing light olefins through catalytic conversion provided by the invention, comprising:
Light hydrocarbon oil raw material after preheating enters bottom riser reactor, contact with regenerated catalyst while of carrying out catalytic cracking reaction and upwards flow, the reaction oil gas of riser reactor outlet and reclaimable catalyst enter cyclonic separator and carry out gas solid separation, isolated reaction oil gas caterpillar, is separated further and obtains the reaction product such as ethene, propylene, C2 ~ C3 alkane and C4 hydrocarbon fraction; Isolated reclaimable catalyst enters coke burning regeneration in catalyst regenerator after stripping, recycles in the regenerated catalyst Returning reactor of activity recovery; Described riser reactor is arranged at catalyst regenerator inside and runs through catalyst regenerator, described riser reactor outlet cyclonic separator, the gaseous phase outlet of cyclonic separator is communicated with subsequent separation system through collection chamber, it is inner that cyclonic separator solid-phase outlet is communicated with catalyst regenerator through stripping stage, and described stripping stage top does not arrange settling vessel.
In method provided by the invention, the operational condition of described riser reactor is: temperature of reaction is 500 ~ 750 DEG C, preferably 540 ~ 720 DEG C, more preferably 560 ~ 700 DEG C, reaction times is 1 ~ 10 second, preferably 2 ~ 6 seconds, more preferably 2 ~ 4 seconds, apparent pressure is 0.05 ~ 1.0MPa, and agent weight of oil ratio is 1 ~ 100, preferably 10 ~ 50, more preferably 20 ~ 40.
The beneficial effect of the method for light hydrocarbon oil producing light olefins through catalytic conversion provided by the invention is:
Have employed riser reactor and be placed in structure in revivifier, save energy, slow down the not enough and thermal balance question that brings of light hydrocarbon oil cracking green coke simultaneously.Riser reactor outlet does not arrange settling vessel, reaction oil gas directly carries out gas solid separation through cyclonic separator, quick derivation oil gas, avoid due to catalyzer and the long and non-selective reaction caused reaction product duration of contact, improve productivity of low carbon olefin hydrocarbon, wherein ethylene yield can reach 24.92 heavy %, and productivity of propylene reaches 26.17 heavy %.
Accompanying drawing explanation
Accompanying drawing is the method flow schematic diagram of light hydrocarbon oil producing light olefins through catalytic conversion provided by the invention.
Wherein: 1-riser reactor, 2-cyclonic separator, 3-catalyst regenerator, 4-regenerated catalyst degassing vessel, 8-catalyst regenerator main air entrance, 9-stripped vapor entrance, 10-reclaimable catalyst standpipe, 11-cyclonic separator gaseous phase outlet pipe, 12-collection chamber, 13-regenerated catalyst inclined tube, 18-separation column, 5,6,7,14,15,16,17,19,20,21,22,23,24,25-pipeline.
Embodiment
Below illustrate the embodiment of method provided by the invention:
The regenerated catalyst being rich in mesopore zeolite enters the pre lift zone of riser reactor, upwards flow under the effect of pre-lift medium, light hydrocarbon oil raw material after preheating is injecting lift pipe reactor bottom together with atomizing steam, contacts the while of carrying out catalytic cracking reaction upwards flow with regenerated catalyst; The rear logistics of reaction enters cyclonic separator through riser reactor outlet and carries out gas solid separation, isolated reaction oil gas caterpillar, is separated further and obtains the products such as ethene, propylene, C2 ~ C3 alkane and C4; The reclaimable catalyst of isolated band charcoal directly enters the stripping stage of cyclonic separator lower end, enters coke burning regeneration in catalyst regenerator after stripping, and the regenerated catalyst of activity recovery returns in riser reactor and recycles;
Described riser reactor is arranged at catalyst regenerator inside and runs through catalyst regenerator, described riser reactor outlet is directly communicated with cyclonic separator, the gaseous phase outlet of cyclonic separator is communicated with subsequent separation system through collection chamber, it is inner that cyclonic separator solid-phase outlet is directly communicated with catalyst regenerator through stripping stage, and described stripping stage top does not arrange settling vessel.
In method provided by the invention, the operational condition of described riser reactor is: temperature of reaction is 500 ~ 750 DEG C, preferably 540 ~ 720 DEG C, more preferably 560 ~ 700 DEG C, reaction times is 1 ~ 10 second, preferably 2 ~ 6 seconds, more preferably 2 ~ 4 seconds, apparent pressure is 0.05 ~ 1.0MPa, agent weight of oil ratio (agent-oil ratio) is 1 ~ 100, preferably 10 ~ 50, more preferably 20 ~ 40, and the weight ratio of water vapor and stock oil is 0.05 ~ 1.0.
In method provided by the invention, described light hydrocarbon oil raw material to be boiling range the be hydrocarbon fraction of 25-204 DEG C.One or more in catalytic cracking gasoline, catalytically cracked gasoline, virgin naphtha, coker gasoline, pyrolysis gasoline, pressure gasoline and hydrogenated gasoline can be selected from.
In method provided by the invention, the mode in riser reactor introduced by light hydrocarbon oil raw material, at a feed entrance point, whole described light hydrocarbon oil stock oil can be introduced in reactor, or at least two different feed entrance points, described light hydrocarbon oil raw material be introduced in reactor according to identical or different ratio.
In method provided by the invention, described reaction oil gas enters subsequent separation system, is separated further and obtains ethene, propylene, C2 ~ C3 alkane, C4 hydrocarbon-fraction, gasoline fraction and diesel oil distillate; Preferred scheme is introduced in reactor by isolated C4 hydrocarbon-fraction to carry out freshening.Wherein, light hydrocarbon oil raw material can be introduced in reactor in identical position or different feed entrance points from C4 hydrocarbon-fraction.In a more preferred embodiment, the described C4 hydrocarbon-fraction returning riser reactor introduces reactor after described light hydrocarbon oil feedstock position.
In method provided by the invention, with the total weight of catalyzer, described catalyzer contains: the heavy % of the heavy % of zeolite 1 ~ 60, the heavy % of inorganic oxide 5 ~ 99 and clay 0 ~ 70, its mesolite is as active ingredient, be selected from mesopore zeolite and optional large pore zeolite, mesopore zeolite accounts for 50 ~ 100 heavy % of zeolite gross weight, preferably 70 ~ 100 heavy %, large pore zeolite accounts for 0 ~ 50 heavy % of zeolite gross weight, preferably 0 ~ 30 heavy %.
Described mesopore zeolite is selected from the zeolite with MFI structure, such as ZSM-5 zeolite and/or ZRP zeolite, also modification can be carried out to transition metals such as the non-metallic elements such as above-mentioned mesopore zeolite phosphorus and/or iron, cobalt, nickel, about the more detailed description of ZRP is see US5232675, about the more detailed description of ZSM-5 is see US3702886.One or more in the overstable gamma zeolite that described large pore zeolite is selected from Rare Earth Y (REY), rare earth hydrogen Y (REHY), different methods obtain.Described inorganic oxide, as caking agent, is selected from silicon-dioxide (SiO
2) and/or aluminium sesquioxide (Al
2o
3).Described clay, as matrix (i.e. carrier), is selected from kaolin and/or halloysite.
In method provided by the invention, described reaction oil gas enters subsequent separation system, such as separation column, is separated further and obtains dry gas, liquefied gas, gasoline fraction and diesel oil distillate.Dry gas and liquefied gas be separated further through gas separation equipment and obtain ethene, propylene, C2 ~ C3 alkane, C4 hydrocarbon-fraction, from reaction product, separating ethene is similar to this area convenient technical process with methods such as propylene, and the present invention is not limited in this respect.
In method provided by the invention, in described catalyst regenerator, outside the reclaimable catalyst standpipe that stripping stage bottom connects, cylindrical central sleeve is set, described cylindrical central sleeve upper end outer rim is provided with the catalyzer guide plate under being tilted to, described reclaimable catalyst standpipe bottom arranges plug valve, and plug valve valve head hits exactly with regeneration standpipe and aligns.Reclaimable catalyst after stripping is got off through regeneration standpipe by stripping stage, cylindrical central sleeve is entered after plug valve adjust flux, carry the conveying of wind bottom cylindrical central sleeve under, centrally sleeve rises, and enters revivifier inner catalyst dense bed middle and upper part by the catalyzer guide plate of cylindrical central sleeve upper end.Catalyst regenerator bottom arranges described cylindrical central sleeve and plug valve can prevent the oxygen-containing gas in catalyst regenerator from entering stripping stage, and plug valve can control reclaimable catalyst flow simultaneously.
In catalyst regenerator, the flue gas generated after catalyzer coke burning regeneration is in catalyst regenerator top gas solid separation, and such as, after cyclonic separator gas solid separation, isolated regenerated flue gas discharge catalyst regenerator enters aftertreatment systems and processes further.
In method provided by the invention, in described catalyst regenerator, the regenerated catalyst of coke burning regeneration is introduced in degassing vessel, introduce riser reactor bottom cycle after removing oxygen-containing gas to use, in the oxygen-containing gas return catalizer revivifier that degassing vessel top removes, riser reactor is entered to avoid a large amount of regenerated flue gas, finally arrive absorbing-stabilizing system, pneumatic press, increase unnecessary energy expenditure.
Compared with prior art, the advantage of the method for light hydrocarbon oil raw material catalytic cracking production low-carbon alkene provided by the invention is:
(1) employing riser reactor is placed in the structure in revivifier, reduce the heat radiation total surface area of reactor and revivifier, avoid the radiation energy consumption of reactor, decrease quantity of supplementary fuel, save energy, meanwhile, built-in riser reactor also can obtain heat from revivifier, slow down the not enough and thermal balance question that brings of light hydrocarbon oil cracking green coke.
(2) settling vessel of traditional catalytic cracking unit is eliminated, adopt the cyclonic separator with stripper, shorten the duration of contact of oil gas and catalyzer, quick derivation oil gas, decrease the oil gas residence time, decrease catalyzer and reaction product at the non-selective secondary reaction of settling section, improve productivity of low carbon olefin hydrocarbon, wherein ethylene yield can reach 24.92 heavy %, and productivity of propylene reaches 26.17 heavy %.
(3) reactor is integrated with revivifier, and be placed in by reactor in revivifier, structure is simple and compact, greatly saves cost of equipment and construction investment.
Adopt method provided by the invention, refinery can produce ethene and propylene to greatest extent from light hydrocarbon oil, realize refinery to change to chemical industry type from traditional fuel type and fuel-Lube Type refinery production model, both solved the problem of petrochemical material shortage, turn improved the economic benefit of refinery.
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 the schematic flow sheet of the catalysis conversion method of light hydrocarbon oil raw material production low-carbon alkene provided by the invention.As shown in drawings, pre-lift medium enters by bottom riser reactor 1 through pipeline 5, from the regenerated catalyst of pipeline 14 under the castering action of pre-lift medium along riser tube upwards accelerated motion, raw material after pipeline 7 mixes with the atomization/dilution steam generation from pipeline 6 in nozzle injecting lift pipe reactor 1, with the catalyst mix in riser reactor, catalytic conversion reaction is there is in stock oil on the catalyzer of heat, and upwards accelerated motion.The reaction oil gas of riser reactor outlet and the reclaimable catalyst of carbon deposit enter the cyclonic separator 2 with stripper, cyclonic separator can be two-stage, to improve gas-solid disngaging efficiency, realize being separated of reclaimable catalyst and reaction product oil gas, reaction product oil gas enters collection chamber 12 through cyclone separator outlet pipe 11, and the reaction product oil gas in collection chamber 12 enters subsequent separation system through pipeline 17 and is separated further.
Reclaimable catalyst after cyclonic separator 2 is separated directly enters stripping stage, contacts stripping remove the oil gas that reclaimable catalyst adsorbs with the stripped vapor from pipeline 9.The reaction oil gas that stripping goes out from reclaimable catalyst enters collection chamber 12 after cyclonic separator 2.Reclaimable catalyst after stripping gets off through reclaimable catalyst standpipe 10, after being arranged at plug valve 33 adjust flux bottom regeneration standpipe 10, to enter in the center sleeve 34 being arranged at regeneration standpipe 15 outside and to be folded to top, centrally the catalyzer guide plate 35 of sleeve pipe 34 top outer rim returns in catalyst regenerator again, main air containing oxygen enters regenerator bottoms through pipeline 8, coke on burning-off reclaimable catalyst, makes reclaimable catalyst regenerate activity recovery.Catalyzer after regeneration enters degassing vessel 4 through regenerator sloped tube 13, and the regenerated catalyst after degassed is recycled to bottom riser reactor 1 through pipeline 14, and the gas on degassing vessel top returns in revivifier 3 through pipeline 15.
Reaction product oil gas in collection chamber 12, through pipeline 17, enters follow-up separation system 18, is separated the catalytic pyrolysis hydrogen, methane and the ethene that obtain and draws through pipeline 19, obtains object product ethylene through being separated further; Ethane and propane are drawn through pipeline 20; Propylene is drawn through pipeline 21 and is obtained object product propylene; And C4 hydrocarbon fraction is drawn through pipeline 22, return riser reactor 1, C4 hydrocarbon fraction and can mix with light hydrocarbon oil raw material through pipeline 7 injecting lift pipe 1, also can through pipeline 25 injecting lift pipe 1 together with the atomizing steam from pipeline 16; Catalytic cracking gasoline is drawn through pipeline 23; Diesel oil is drawn through pipeline 24.
The following examples will be further described present method, but therefore not limit present method.
Raw material used in embodiment is virgin naphtha, and its character is as shown in table 1.
Catalytic cracking catalyst preparation method used in embodiment is summarized as follows:
1) by 20gNH
4cl is dissolved in 1000g water, and in this solution, adding 100g (butt) crystallization product ZRP-1 zeolite, (Qilu Petrochemical Company's catalyst plant is produced, SiO
2/ Al
2o
3=30, content of rare earth RE
2o
3=2.0 heavy %), after exchanging 0.5h at 90 DEG C, filter to obtain filter cake; Add 4.0gH
3pO
4(concentration 85%) and 4.5gFe (NO
3)
3be dissolved in 90g water, dry with filter cake hybrid infusion; Then within 2 hours, obtain phosphorous and MFI structure mesopore zeolite that is iron 550 DEG C of roasting temperature process, its elementary analytical chemistry consists of
0.1Na
2O·5.1Al
2O
3·2.4P
2O
5·1.5Fe
2O
3·3.8RE
2O
3·88.1SiO
2。
2) use 250kg decationized Y sieve water by 75.4kg halloysite (Suzhou china clay company Industrial products, the heavy % of solid content 71.6) making beating, add 54.8kg pseudo-boehmite (Shandong Aluminum Plant's Industrial products, the heavy % of solid content 63) again, with hydrochloric acid, its PH is adjusted to 2 ~ 4, stir, at 60 ~ 70 DEG C, leave standstill aging 1 hour, keep PH to be 2 ~ 4, cool the temperature to less than 60 DEG C, add 41.5kg Alumina gel (Qilu Petrochemical Company's catalyst plant product, Al
2o
3content is 21.7 heavy %), stir 40 minutes, obtain mixed serum.
3) by step 1) the MFI structure mesopore zeolite (butt is 22.5kg) of phosphorous and iron prepared and DASY zeolite (Qilu Petrochemical Company's catalyst plant Industrial products, lattice constant is 2.445 ~ 2.448nm, butt is 2.0kg) join step 2) in the mixed serum that obtains, stir, spray drying forming, with ammonium dihydrogen phosphate (phosphorus content is 1 heavy %) washing, wash away free Na
+, be drying to obtain catalytic cracking catalyst sample, the MFI structure mesopore zeolite consisting of the phosphorous and iron of 18 heavy % of this catalyzer, 2 heavy %DASY zeolites, 28 heavy % pseudo-boehmites, 7 heavy % Alumina gel and balance kaolin.
Embodiment
This embodiment is tested according to the flow process of accompanying drawing, take virgin naphtha as raw material, the middle-scale device of riser reactor is tested, the stock oil of preheating enters bottom riser tube, temperature of reaction 675 DEG C, 2.5 seconds reaction times, the weight ratio 30 of catalytic cracking catalyst and stock oil, the weight ratio of water vapor and stock oil is carry out cracking reaction under 0.45 condition, reaction product and water vapour and reclaimable catalyst enter closed cyclone separator from reactor outlet, reaction product and catalyzer sharp separation, reaction product by with raw material heat exchange after cut by boiling range in separation system, thus obtain dry gas, propylene, the cuts such as carbon four and gasoline, wherein carbon four returns and enters the further cracking of reactor is ethene and propylene.Reclaimable catalyst enters stripper under gravity, is gone out the hydrocarbon product that reclaimable catalyst adsorbs by water vapour stripping, and the reclaimable catalyst after stripping enters into revivifier, contacts regenerate with air.Catalyzer after regeneration enters degassing vessel, with the non-hydrocarbon gas impurity removing regenerated catalyst absorption and carry.Regenerated catalyst after stripping turns back in riser tube reaction again and recycles.Operational condition and product slates list in table 2.
As can be seen from Table 2, ethylene yield can reach 24.92 heavy %, and productivity of propylene can reach 26.17 heavy %, and propylene/ethylene ratio is about 1.05.
Table 1
| Stock oil character | |
| Density (20 DEG C), g/cm 3 | 0.7358 |
| Vapour pressure/kPa | 50.0 |
| Group composition/weight % | |
| Paraffinic hydrocarbons | 51.01 |
| Naphthenic hydrocarbon | 38.24 |
| Alkene | 0.12 |
| Aromatic hydrocarbons | 10.52 |
| Boiling range, DEG C | |
| IBP | 46 |
| 10％ | 87 |
| 30％ | 107 |
| 50％ | 120 |
| 70％ | 133 |
| 90％ | 149 |
| 95％ | 155 |
Table 2
| Operational condition | |
| Outlet temperature of riser, DEG C | 675 |
| Reaction times, second | 2.5 |
| The weight ratio of water vapor/raw material | 0.45 |
| Agent-oil ratio (weight ratio) | 30 |
| Product slates, heavy % | |
| Hydrogen+methane | 15.78 |
| Ethene | 24.92 |
| Propylene | 26.17 |
| Ethane+propane | 14.01 |
| Gasoline | 15.48 |
| Diesel oil | 1.58 |
| Coke | 2.06 |
| Add up to | 100.00 |
Claims (12)
1. the method for light hydrocarbon oil producing light olefins through catalytic conversion, comprising:
Light hydrocarbon oil raw material after preheating enters bottom riser reactor, contact with regenerated catalyst while of carrying out catalytic cracking reaction and upwards flow, the reaction oil gas of riser reactor outlet and reclaimable catalyst enter cyclonic separator and carry out gas solid separation, isolated reaction oil gas caterpillar, is separated further and obtains ethene, propylene, C2 ~ C3 alkane and C4 hydrocarbon fraction and other products; Isolated reclaimable catalyst enters coke burning regeneration in catalyst regenerator after stripping, recycles in the regenerated catalyst Returning reactor of activity recovery;
It is characterized in that, described riser reactor is arranged at catalyst regenerator inside and runs through catalyst regenerator, described riser reactor outlet cyclonic separator, the gaseous phase outlet of cyclonic separator is communicated with subsequent separation system through collection chamber, it is inner that cyclonic separator solid-phase outlet is communicated with catalyst regenerator through stripping stage, and described stripping stage top does not arrange settling vessel; In described catalyst regenerator, outside the reclaimable catalyst standpipe that stripping stage bottom connects, cylindrical central sleeve is set, described cylindrical central sleeve upper end outer rim is provided with the catalyzer guide plate under being tilted to, described reclaimable catalyst standpipe bottom arranges plug valve, and plug valve valve head hits exactly with reclaimable catalyst standpipe and aligns.
2. according to the method for claim 1, it is characterized in that, the operational condition of described riser reactor is: temperature of reaction is 500 ~ 750 DEG C, reaction times is 1 ~ 10 second, apparent pressure is 0.05 ~ 1.0MPa, the weight ratio of catalyzer and stock oil is 1 ~ 100, and the weight ratio of water vapor and stock oil is 0.05 ~ 1.0.
3. according to the method for claim 2, it is characterized in that, the operational condition of described riser reactor is: temperature of reaction is 540 ~ 720 DEG C, and the reaction times is 2 ~ 6 seconds, and the weight ratio of catalyzer and stock oil is 10 ~ 50.
4. according to the method for claim 3, it is characterized in that, the operational condition of described riser reactor is: temperature of reaction is 560 ~ 700 DEG C, and the reaction times is 2 ~ 4 seconds, and the weight ratio of catalyzer and stock oil is 20 ~ 40.
5. according to any one method in claim 1-4, it is characterized in that, the operational condition of described catalyst regenerator is: regeneration temperature is 550 ~ 750 DEG C, and fluidized bed gas apparent linear velocity is 0.8 ~ 3.0 meter per second, and catalyzer mean residence time is 0.6 ~ 2.0 minute.
6. according to any one method in claim 1-4, it is characterized in that, the C4 hydrocarbon fraction described in reaction product is returned in riser reactor and continue reaction.
7. according to the method for claim 6, it is characterized in that, the described C4 hydrocarbon-fraction returning riser reactor introduces riser reactor after described light hydrocarbon oil feedstock position.
8. according to any one method in claim 1-4, it is characterized in that, with the total weight of catalyzer, in described catalyzer: the content of zeolite is 1 ~ 60 heavy %, the content of inorganic oxide is 5 ~ 99 heavy %, the content of clay is 0 ~ 70 heavy %, its mesolite is selected from mesopore zeolite and optional large pore zeolite, and mesopore zeolite accounts for 50 ~ 100 heavy % of zeolite gross weight, and large pore zeolite accounts for 0 ~ 50 heavy % of zeolite gross weight.
9. according to the method for claim 8, it is characterized in that, described mesopore zeolite accounts for 70 ~ 100 heavy % of zeolite gross weight, and large pore zeolite accounts for 0 ~ 30 heavy % of zeolite gross weight.
10. according to any one method in claim 1-4, it is characterized in that, described light hydrocarbon oil raw material to be boiling range the be hydrocarbon fraction of 25-204 DEG C.
11. according to the method for claim 10, it is characterized in that, described light hydrocarbon oil raw material is selected from the mixture of one or more in catalytic cracking gasoline, catalytically cracked gasoline, virgin naphtha, coker gasoline, pyrolysis gasoline, pressure gasoline and hydrogenated gasoline.
12. according to any one method in claim 1-4, and the regenerated catalyst from catalyst regenerator enters degassing vessel, and the regenerated catalyst after degassed returns riser reactor bottom cycle and uses, in the oxygen-containing gas return catalizer revivifier on degassing vessel top.
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| CN105439798B (en) * | 2014-08-19 | 2018-06-19 | 中国石油化工股份有限公司 | The method that light petroleum hydrocarbon catalytic pyrolysis produces ethylene and propylene |
| CN116554923A (en) * | 2022-01-28 | 2023-08-08 | 中国石油化工股份有限公司 | Method and system for producing low-carbon olefin by heavy oil |
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| CN102041032A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Coaxial type compounding lifting pipe circular reaction-regenerating device |
| CN102039107A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Parallel cyclic reaction-regeneration device with embedded riser |
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| CN102041032A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Coaxial type compounding lifting pipe circular reaction-regenerating device |
| CN102039107A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Parallel cyclic reaction-regeneration device with embedded riser |
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