CN101857520B - Method for increasing yield of propylene and ethylene - Google Patents
Method for increasing yield of propylene and ethylene Download PDFInfo
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- CN101857520B CN101857520B CN2009100817670A CN200910081767A CN101857520B CN 101857520 B CN101857520 B CN 101857520B CN 2009100817670 A CN2009100817670 A CN 2009100817670A CN 200910081767 A CN200910081767 A CN 200910081767A CN 101857520 B CN101857520 B CN 101857520B
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Abstract
The invention relates to a method for increasing yield of propylene and ethylene in the steam cracking process. The steam cracking process is performed through a cracking furnace and a separation system; and on the basis, a catalytic cracking system which takes C4 fraction produced in an oil refining process, C4 fraction produced in the steam cracking process and/or catalytic cracking gasoline produced in the oil refining process as a raw material is increased; the mixture of C4 olefine and alkane and/or the catalytic cracking gasoline are/is completely or partially converted into the cracked gas containing rich propylene and ethylene through the catalytic cracking system; and the separation and purification of an objective product are mainly finished by the separation system in the steam cracking process. The method is characterized by making the most of the potential of the separation (recovery) system in the steam cracking; only the catalytic cracking system consisting of a catalytic cracking reactor and a simple separation device is increased; and the method increases the yield of low carbon olefins such as propylene, ethylene and the like and contributes to improving the economic benefit of enterprises.
Description
Technical field
The present invention relates to the method for a kind of propylene enhancing, ethene, more particularly, the present invention relates to a kind of method of utilizing existing preparing ethylene by steam cracking device and tripping device to improve propylene and ethylene yield.
Background technology
At present, the main mode of production of the low-carbon alkene such as ethene, propylene is steam cracking/thermo-cracking in the world, steam cracking process by pyrolyzer with separate (recovery) system two portions and consist of.In steam cracking process, cracking stock and water vapor mixture are heated to high temperature and carry out heat scission reaction in pyrolyzer, the splitting gas of ethene, propylene is rich in generation, then this splitting gas is sent in separation (recovery) system to carry out separating-purifying, obtained the cracking products such as ethene, propylene.
In recent years, rapid growth along with domestic economy, the market requirement of the low-carbon alkene such as ethene, propylene is increasing, and domestic ethene, the original throughput of propylene can not satisfy the market requirement that increases rapidly, so China all wants a large amount of ethene of import, propylene every year.For alleviating the disparities between supply and demand of state's inner propene, Market for Ethylene, fill up demand gap, China recent years has started continuously second and third and has taken turns the reconstruction and extension project of ethylene industry.Comprehensive various report, before 2010, the olefin plant of tens scales 80～1,200,000 tons of ethene/years will appear in China.In a foreseeable future, the imbalance between supply and demand in the low-carbon alkene markets such as state's inner propene, ethene will be eased.It should be noted that, these scales all belong to traditional steam crack material at the employed cracking stock of olefin plant in 80～1,200,000 tons of ethene/years, such as petroleum naphtha, hydrogenation tail oil, lighter hydrocarbons etc., and supporting crude capacity does not obtain corresponding raising with it, may cause traditional cracking stock shortage or cracking stock quality to descend, thereby make separation (recovery) system in the steam cracking process in actual production, may have larger operation surplus.Therefore, propylene, ethylene yield become an important factor that affects Business Economic Benefit in the steam cracking process to improve how to enlarge raw material sources.
What at first cause concern is, in the split product of steam cracking process process, except main purpose product ethene, propylene, divinyl, aromatic hydrocarbons, generally also contain C 4 olefin and the paraffins mixture of 4～10 (weight) %, wherein about 70 (weight) % is above is butylene.For this part C 4 olefin and paraffins mixture, often to use as city domestic fuel liquefied petroleum gas (LPG), economic worth is relatively low.Along with country " the progressively realization of West-east Gas engineering; city domestic fuel liquefied petroleum gas (LPG) also will be replaced by the more cheap Sweet natural gas of price, thus in the split product this part C 4 olefin and paraffins mixture be badly in need of seeking new, added value is higher utilizes approach.For above-mentioned situation, each large petro-chemical corporation drops into one after another strength and develops carbon four and carbon four above low value alkene alkane and produce technique and the catalyzer of the low-carbon alkenes such as ethene, propylene in the world, and has obtained satisfied result.By Chinese patent CN1915933A as can be known, in C 4 olefin and paraffins mixture catalytic pyrolysis process, product mainly is hydrogen, methane, carbon two, carbon three, carbon four, and all the other are C
5-C
12The aromatic hydrocarbons that chain type alkane and alkene and 1% (weight) are following.As seen, product composition in the product composition of C 4 olefin and paraffins mixture catalytic pyrolysis process and distribution and the steam cracking process distributes basically identical, can adopt with steam cracking process in identical separating (recovery) system carry out separating-purifying and obtain the cracking product.
In addition, the certain situation in the gasoline production process also merits attention: in the past few years, for protection of the environment, in the world wide motor spirit has been proposed higher index.Different from world other countries, the catalytically cracked gasoline that accounts for China's gasoline consumption 40% needs because its olefin(e) centent is higher to improve.A kind of way is that the temperature and the catalyst performance that improve catalytic cracking process reduce olefin(e) centent, and another kind of way is the catalytically cracked gasoline that has produced to be reduced the processing of olefin(e) centent.In conjunction with the composition of catalytically cracked gasoline and bibliographical information as can be known, to form in the catalytic pyrolysis process of similar raw material with catalytically cracked gasoline, product comprises hydrogen, methane, ethane, ethene, propane, propylene, carbon four and carbon four above alkene paraffins mixture and a small amount of aromatic hydrocarbons.As seen, product composition and the product composition in the steam cracking process of catalytically cracked gasoline catalytic cracking reaction are basically identical, can adopt with steam cracking process in (recovery) system that separates carry out separating-purifying and obtain propylene and ethylene product.
Summary of the invention
The present invention is in order to alleviate the imbalance between supply and demand in the low-carbon alkene markets such as state's inner propene and ethene, and having proposed increases the system of C-4-fraction and/or refinery's pyrolysis gasoline catalytic pyrolysis preparing ethylene and propylene so that the method for propylene and ethylene yield to be provided in existing steam cracking device.
Method provided by the invention, based on the basically identical characteristics of the product composition of the catalytic cracking reaction of the catalytically cracked gasoline that produces in the C-4-fraction that produces in the C-4-fraction that produces in the oil refining process and/or the steam cracking process and/or the oil refining process and the product composition in the steam cracking process, advantage in conjunction with steam cracking process process and catalytic pyrolysis process, fully excavate the potentiality of separating (recovery) system in the existing steam cracking process, outside existing steam cracking process, increase a catalytic pyrolysis system, the catalytically cracked gasoline that produces in the C-4-fraction that produces in the C-4-fraction that produces in the oil refining process and/or the steam cracking process and/or the oil refining process is as raw material, by catalytic cracking reaction above these are mainly C 4 olefin and paraffins mixture or carbon four and are rich in propylene to the material conversion generation of carbon nine alkane and alkene mixture, then the catalytically cracked gas of ethene carries out passing into after the simple separation separation (recovery) system in the steam cracking process to catalytically cracked gas.So just can be by increasing the catalytically cracked gasoline that produces in the C 4 olefin that produces in a C 4 olefin that produces in the oil refining process and paraffins mixture and/or the steam cracking process and paraffins mixture and/or the oil refining process as the catalytic pyrolysis system of raw material, to improve the output of propylene, ethene in the steam cracking process.
Concrete technical scheme is as follows:
The method of propylene enhancing provided by the invention and ethene is in steam cracking and tripping device thereof, increases the catalytic pyrolysis system, said method comprising the steps of:
(1) catalytic pyrolysis: with refinery's C-4-fraction and/or cracking c_4 cut and/or catalytically cracked gasoline introducing catalytic pyrolysis system, described raw material is converted at least in part the catalytically cracked gas that is rich in propylene and ethene;
(2) separate: with catalytically cracked gas cooling and the separation that step (1) obtains, each logistics that separates is sent into the appropriate location of the separation of steam cracking, with the propylene of raising steam cracking device and the output of ethene.
Preferably, in step (1), described catalytic pyrolysis system comprises olefins by catalytic cracking unit, mixed olefins and alkane catalytic pyrolysis unit and separating unit.
More preferably, in step (1), in described olefins by catalytic cracking unit, described raw material is converted into the catalytically cracked gas logistics 1 that is rich in propylene and ethene at least in part, cooling and through separating, obtain the logistics 2 of carbon three following cuts and the logistics 3 of carbon four above cuts, described mixed olefins and alkane catalytic pyrolysis unit are sent in the logistics 3 of carbon four above cuts, in described mixed olefins and alkane catalytic pyrolysis unit, the logistics 3 of described carbon four above cuts is converted at least in part and is rich in propylene, the catalytically cracked gas logistics 4 of ethene, with logistics 4 coolings and through separating, obtain the logistics of carbon three following cuts, its logistics 2 with carbon three following cuts is sent in the separate part of steam cracking device, with the propylene of raising steam cracking device and the output of ethene.
Further preferably, after described catalytically cracked gas logistics 1 cooling, be separated into first the logistics of carbon five following cuts and the logistics of carbon six above cuts, then the logistics of carbon five following cuts is separated into logistics 2 and carbon four carbon five mixed fraction of carbon three following cuts, the logistics with carbon six above cuts mixes to enter described mixed olefins and alkane catalytic pyrolysis unit with carbon four carbon five mixed fraction again; After described catalytically cracked gas logistics 4 coolings, be separated into first the logistics of carbon six above cuts and the logistics of carbon five following cuts, then the logistics of carbon five following cuts isolated the logistics of carbon three following cuts.
The logistics that comprises ethene and propylene that produces for the catalytic pyrolysis system, preferably, described catalytic pyrolysis system produces and the logistics of isolated carbon three following cuts is sent in the splitting gas of oil scrubber, water wash column or compressor of steam cracking separation system.
The C-4-fraction that produces for catalytic pyrolysis, preferably, described catalytic pyrolysis system produce and isolated C-4-fraction recycle or deliver to liquefied petroleum gas (LPG) or the torch pipeline in.
The cut of carbon five or more that produces for catalytic pyrolysis, preferably, described catalytic pyrolysis system produces the logistics recycle of isolated carbon five above cuts also or delivers to the pyrolysis gasoline hydrogenation device.
For the cooling in the catalytic pyrolysis system with separate, preferably, it is 0～100 ℃ that catalytically cracked gas cools off with the temperature range of separating, preferred 0～40 ℃.
Preferably, the catalyzer that uses of described catalytic pyrolysis system is one or more of modification or unmodified SAPO-34, ZSM-5, ZSM-11, ZSM-23, MCM-22, MCM-49, MCM-56 and mordenite.
Preferably, the temperature of reaction of described olefins by catalytic cracking unit is 400～600 ℃, and reaction pressure is 0.07～0.50MPa, and volume space velocity is 0.5～100h during reaction solution
-1, the charging mass ratio of water vapour and catalytic pyrolysis raw material is 0～10; The temperature of reaction of described mixed olefins and alkane catalytic pyrolysis unit is 450～650 ℃, and reaction pressure is 0.07～0.50MPa, and volume space velocity is 0.5～100h during reaction solution
-1, the charging mass ratio of water vapour and catalytic pyrolysis raw material is 0～10.
The pyrolyzer of the present invention in existing steam cracking process process with separate (recovery) system outside, increase the catalytically cracked gasoline that produces in the C 4 olefin that produces in a C 4 olefin that produces in the oil refining process and paraffins mixture and/or the steam cracking process and paraffins mixture and/or the oil refining process and be the catalytic pyrolysis system of raw material, take C 4 olefin and paraffins mixture and/or catalytically cracked gasoline as raw material, make it Partial Conversion by catalytic cracking reaction and become to be rich in propylene, the catalytically cracked gas of ethene, and the separating-purifying of this catalytically cracked gas is finished by the separation in the steam cracking process (recovery) system, only needing to increase the catalytically cracked gasoline that produces in the C 4 olefin that produces in a C 4 olefin that produces in the oil refining process and paraffins mixture and/or the steam cracking process and paraffins mixture and/or the oil refining process as the catalytic pyrolysis system of raw material in existing steam cracking process, is to improve propylene in the existing steam cracking process, a kind of practicable method of ethylene yield.
The catalytically cracked gasoline that produces in the C 4 olefin that produces in the C 4 olefin that produces in the oil refining process and paraffins mixture and/or the steam cracking process and paraffins mixture and/or the oil refining process is comprised of two class catalytic cracking reaction devices as the catalytic pyrolysis system of raw material.The catalytic cracking reaction device is to be made of olefins by catalytic cracking reactor and mixed olefins and alkane catalytic cracking reaction device.The catalytic cracking reaction device can be one or more combination in fixed bed, moving-bed, the fluidized-bed.Raw material in the catalytic pyrolysis system is a kind of logistics of the catalytically cracked gasoline that produces in the C 4 olefin that produces in the C 4 olefin that produces in the oil refining process and paraffins mixture and/or the steam cracking process and paraffins mixture and/or the oil refining process or the mixture of several logistics.
The olefins by catalytic cracking catalyzer can be one or more in all kinds molecular sieve catalysts such as modification or unmodified SAPO-34, ZSM-5, ZSM-11, ZSM-23, MCM-22, MCM-49, MCM-56, mordenite.The olefins by catalytic cracking catalyzer can be with the some or all of catalytically cracked gas that is rich in propylene, ethene that is converted into of the alkene component in this patent raw material.Olefins by catalytic cracking catalyst reaction temperatures scope is 400-600 ℃, and reaction pressure (gauge pressure) scope is 0.07-0.50Mpa, and water and weight of material ratio are 0-10, and material feeding air speed scope is 0.5-100 hour
-1
Mixed olefins and alkane catalytic cracking catalyst can be one or more in all kinds molecular sieve catalysts such as modification or unmodified SAPOZSM-5, ZSM-11, ZSM-23, MCM-22, MCM-49, MCM-56, mordenite.Mixed olefins and alkane catalytic cracking catalyst can be converted into the catalytically cracked gas that is rich in propylene, ethene in whole or in part with the carbon four in the catalytic pyrolysis raw material to carbon nine alkene and paraffins mixture.Mixed olefins and alkane catalytic cracking catalyst range of reaction temperature are 500-750 ℃, and reaction pressure (gauge pressure) scope is 0.07-0.50Mpa, and water and weight of material ratio are 0-10, and material feeding air speed scope is 0.5-100 hour
-1
The raw material that the catalytic pyrolysis system uses can be a kind of logistics of the catalytically cracked gasoline that produces in the C 4 olefin that produces in the C 4 olefin that produces in the oil refining process and paraffins mixture and/or the steam cracking process and paraffins mixture and/or the oil refining process or the mixture of several logistics.
In sum, in steam cracking process, add the catalytically cracked gasoline that produces in the C 4 olefin that produces in the C 4 olefin that produces in the oil refining process and paraffins mixture and/or the steam cracking process and paraffins mixture and/or the oil refining process in the catalytic pyrolysis system of raw material, catalytic pyrolysis product in this catalytic pyrolysis system is carried out initial gross separation, and the product that separates is passed into respectively the corresponding position of separation (recovery) system in the steam cracking process, thereby improved propylene and ethylene yield, increased the economic benefit of enterprise.
Embodiment
Further describe the present invention below in conjunction with embodiment.Scope of the present invention is not limited by these embodiment.
Comparative example 1
The olefin plant of certain 1,000,000 ton/years of ethene has 11 pyrolyzer, and wherein 6 is the light oil cracking stove, 3 heavy oit pyrolysis stoves, and 1 is the light hydrocarbon cracking stove, one is pyrolyzer for subsequent use.The light oil cracking stove is take naphtha cracking as main, and the heavy oit pyrolysis stove is cracked into the master with hydrogenation tail oil, and the light hydrocarbon cracking stove is take cycle ethane and Deposition During Propane Pyrolysis as main.Each pyrolyzer charging capacity sees Table 1, and ethene, propylene, butane butylene yield and output see Table 2.
Ten thousand tons of olefin plant cracking stock years of table 1100 are thrown oil mass
| Raw material | Petroleum naphtha | HVGO | Cycle ethane | Recycled propane |
| Charging capacity, ten thousand ton/years | 228.00 | 90.00 | 19.35 | 2.66 |
Table 2,100 ten thousand tons of olefin plant primary products yield and output
| Ultimate production, ten thousand ton/years | Total recovery, wt% | |
| Ethene | 100.262 | 30.97 |
| Propylene | 50.722 | 15.67 |
| Butane | 0.637 | 0.20 |
| Butylene | 15.286 | 4.72 |
By table 1 and table 2 as can be known, these cracking stocks generate mixed pyrolysis gas through pyrolyzer thermo-crackings, mixed pyrolysis gas through the separation system separating-purifying after, can produce every year:
(1) the complete total annual production of factory's ethene is 100.262 ten thousand tons, and full factory ethene total recovery is 30.97%;
(2) the complete total annual production of factory's propylene is 50.722 ten thousand tons, and full factory propylene total recovery is 15.67%;
(3) the complete total annual production of factory's butane is 0.637 ten thousand ton, and the butylene ultimate production is 15.286 ten thousand tons.
(4) butene content is 95.9% in the C 4 olefin paraffins mixture (not containing diolefin), and butane content is 4.1%.
Embodiment 1
On the basis of comparative example 1, increase C 4 olefin and a paraffins mixture in the steam cracking process and be the catalytic pyrolysis system of raw material, this catalytic pyrolysis system mainly is comprised of olefins by catalytic cracking reactor, mixed olefins and alkane catalytic cracking reaction device, and is specific as follows:
(1) at first the butane in the comparative example 1 and butene mixture are passed in the catalytic cracking reaction device 1 (olefins by catalytic cracking reactor), the C 4 olefin in the raw material contacts with alkene catalyst and is 3 hours in 550 ℃ of temperature of reaction, reaction pressure (gauge pressure) 0.15Mpa, air speed
-1Carry out catalytic cracking reaction under the condition, this catalyzer becomes to be rich in the logistics 1 of propylene, ethene with 70% C _ 4 alkene catalytic pyrolysis in the charging, and wherein propylene content is 30.72% in the logistics 1, and ethylene content is 9.6%.This olefins by catalytic cracking catalyzer is with phosphorus and/or alkali-earth metal modified little crystal grain (particle diameter is less than 800 nanometers) ZSM-5 molecular sieve type catalyzer, consisting of of catalyzer: 5wt%P, 2wt%La, 64wt%ZSM-5 molecular sieve (silica alumina ratio is 100, and particle diameter is 500 nanometers) and 29wt% silicon oxide.
(2) logistics 1 is cooled to 20 ℃, separates, obtain logistics 2 and logistics 3, wherein logistics 2 is carbon five following components, and logistics 3 is for containing the carbon six above components of a small amount of carbon five.
(3) logistics 2 is passed in the rectifying tower 1 in this catalytic pyrolysis system and separate, obtain logistics 4 and logistics 5, logistics 4 is carbon three following components, and logistics 5 is carbon four carbon pentaene hydrocarbon paraffins mixtures.
(4) logistics 3 is mixed with logistics 5, obtain logistics 6, logistics 6 is composed as follows:
1) have neither part nor lot in the butane of reaction, its content is 7.56%;
2) unreacted C 4 olefin, its content are 52.47%;
3) content be 25.25% transform the alkene (mainly being that carbon five is to carbon eight) form by C 4 olefin;
4) carbon five is to carbon eight alkane, and its content is 11.80%;
5) aromatic hydrocarbons, its content are 1%.
(5) logistics 6 is passed in the catalytic cracking reaction device 2 (mixed olefins and alkane catalytic cracking reaction device).In catalytic cracking reaction device 2, logistics 6 contacts with alkane cracking catalyst with mixed olefins and is 3 hours in 700 ℃ of temperature of reaction, reaction pressure (gauge pressure) 0.10Mpa, air speed
-1Condition under carry out catalytic cracking reaction, this catalyzer becomes to be rich in the logistics 7 of propylene, ethene to carbon eight alkene and alkane catalytic pyrolysis with most of carbon four in the logistics 6, wherein propylene content is 35.2% in the logistics 7, ethylene content is 11%.Consisting of of this catalyzer: 4wt%P, 3wt%La, 2wt%Ca, 2wt%Ag, 60wt%ZSM-5 molecular sieve (silica alumina ratio is 140, and particle diameter is 400 nanometers) and 29wt% silicon oxide.
(6) with logistics 7 through being cooled to 20 ℃, obtain logistics 8 and logistics 9, logistics 8 is carbon five following components, logistics 9 is for containing the carbon six above components of a small amount of carbon five.
(7) with separating in the rectifying tower 2 in the logistics 8 catalytic pyrolysis systems, obtain logistics 10 and logistics 11, logistics 10 carbon three following components wherein, logistics 11 is carbon four carbon pentaene hydrocarbon and alkane component.
(8) with separating in the rectifying tower 3 of logistics 11 in the catalytic pyrolysis system, obtain logistics 12 and logistics 13, wherein logistics 12 is carbon four components, and logistics 13 is carbon five components.
(9) logistics 13 is mixed with logistics 9, form logistics 14, logistics 14 is carbon five above components.
(10) logistics 14 is passed into the pyrolysis gasoline hydrogenation device.
(11) logistics 12 is passed in the LPG production plant
(13) logistics 10 and logistics 4 mixed after, with its temperature be controlled in 240 ℃ of scopes, pressure is greater than under the 0.7Mpa condition, pass in separation (recovery) system of steam cracking process in the splitting gas pipeline in the oil scrubber.
Calculation result shows, increasing a C 4 olefin that produces in the steam cracking process and paraffins mixture after the catalytic pyrolysis system of raw material, and full factory ethene total recovery is 31.66%, and the propylene total recovery is 17.87%.As previously mentioned, adopt original steam solution technique that is comprised of pyrolyzer and separation system, full factory ethene total recovery is 30.97%, and full factory propylene total recovery is 15.67%.And after increasing the technique that is comprised of steam cracking process, C 4 olefin and paraffins mixture catalytic pyrolysis system, full factory ethene total recovery increases by 0.69%, and the propylene total recovery increases by 2.2%.
Embodiment 2
On the basis of comparative example 1, increase by one take catalytically cracked gasoline as raw material the catalytic pyrolysis system of (raw material form see Table 2), the amount of finish of the pressure gasoline of this catalytic pyrolysis system is 50,000 ton/years, and this catalytic pyrolysis system is made of two catalytic cracking reaction devices, and is specific as follows:
Table 2, catalytically cracked gasoline form
(1) catalytically cracked gasoline is passed in the catalytic cracking reaction device 1 first, the alkene of this catalytically cracked gasoline and specific catalyzer 1 contact reacts, this olefins by catalytic cracking catalyzer is with phosphorus and/or alkali-earth metal modified little crystal grain (particle diameter is less than 800 nanometers) ZSM-5 molecular sieve type catalyzer, consisting of of catalyzer: 5wt%P, 1wt%La, 64wt%ZSM-5 molecular sieve (silica alumina ratio is 100, and particle diameter is 500 nanometers), 30wt% silicon oxide.550 ℃ of temperature of reaction, reaction pressure (gauge pressure) 0.1Mpa, water-oil ratio be 0.5 and air speed be 5 hours
-1Condition under, catalyzer 1 becomes the hydrocarbon fraction catalytic pyrolysis in the charging to be rich in the logistics 1 of propylene, ethene, wherein propylene content is 15% in the logistics 1, ethylene content is 5%.
(2) logistics 1 cooling is separated, logistics 2 is carbon five and carbon five following components, and logistics 3 is carbon five and carbon five above components.Logistics 2 is separated formation logistics 4 and logistics 5 in the intrasystem rectifying tower 1 of catalytic pyrolysis, logistics 4 is carbon three following components, and logistics 5 is carbon four carbon five components.
(3) logistics 5 is mixed with logistics 3 form logistics 6, logistics 6 is passed in the catalytic cracking reaction device 2 in the catalytic pyrolysis system.
(4) in catalytic cracking reaction device 2, logistics 6 contacts with specific catalyzer 2, consisting of of catalyzer 2 these catalyzer: 4wt%P, 3wt%La, 2wt%Ca, 2wt%Ag, 60wt%ZSM-5 molecular sieve (silica alumina ratio is 140, and particle diameter is 400 nanometers), 29wt% silicon oxide.Be that 700 ℃, reaction pressure (gauge pressure) 0.1Mpa, water-oil ratio are 0.5, air speed is 5 hours in temperature of reaction
-1Under the condition, catalyzer 2 generates the logistics 7 that is rich in propylene, ethene with alkene and the paraffin section catalytic pyrolysis of carbon in the logistics 6 more than four, and wherein propylene content is 19% in the logistics 7, and ethylene content is 15%.
(5) logistics 7 coolings are separated formation logistics 8 and logistics 9, logistics 8 is carbon five and carbon five following components, and logistics 9 is carbon five and carbon five above components.
(6) logistics 8 is passed into separate in the rectifying tower 2 in this catalytic pyrolysis system and form logistics 10 and logistics 11, logistics 10 is carbon three following components, and logistics 11 is carbon four carbon five components.
(7) logistics 11 is passed into separate in the rectifying tower 3 in the catalytic pyrolysis system and form logistics 12 and logistics 13, wherein logistics 12 is carbon four components, and logistics 13 is carbon five components.
(8) logistics 4 and logistics 10 mixed, with its temperature be controlled in 240 ℃ of scopes, pressure is greater than under the 0.7Mpa condition, pass in the splitting gas pipeline of oil scrubber of separation (recovery) system in the steam cracking industry.
(9) with separating in the pyrolysis gasoline hydrogenation device in (recovery) system in logistics 13 and the logistics 9 mixing steam cracking technologies.
(10) logistics 12 is passed into the lng production workshop.
According to the calculation of yield of above process, after the catalytic pyrolysis system that increases with the catalytically cracked gasoline raw material, the propene yield of catalytically cracked gasoline reaches 29.284%, and yield of ethene reaches 16.544%.To separate in the catalytically cracked gas, and carbon three following components are passed in the splitting gas pipeline of oil scrubber of separation (recovery) system in the steam cracking process, but thus every year 0.82 ten thousand ton of increasing output of ethylene, propylene increases production 1.46 ten thousand tons.
This shows, in original steam cracking process process, the catalytically cracked gasoline that produces in the C 4 olefin that produces in the C 4 olefin that increase produces in the oil refining process and paraffins mixture and/or the steam heat cracking technology and paraffins mixture and/or the oil refining process is the catalytic pyrolysis system of raw material, in the situation that increase a small amount of catalytic cracking reaction device, full factory's ethene and productivity of propylene are significantly improved, and are conducive to enterprise and increase economic efficiency.
Claims (8)
1. the method for a propylene enhancing and ethene in steam cracking and tripping device thereof, increases the catalytic pyrolysis system, it is characterized in that, said method comprising the steps of:
(1) catalytic pyrolysis: with refinery's C-4-fraction and/or cracking c_4 cut and/or catalytically cracked gasoline introducing catalytic pyrolysis system; Described catalytic pyrolysis system comprises olefins by catalytic cracking unit, mixed olefins and alkane catalytic pyrolysis unit and separating unit; In described olefins by catalytic cracking unit, described raw material is converted into the catalytically cracked gas logistics 1 that is rich in propylene and ethene at least in part, cooling and through separating, obtain the logistics 2 of carbon three following cuts and the logistics 3 of carbon four above cuts, described mixed olefins and alkane catalytic pyrolysis unit are sent in the logistics 3 of carbon four above cuts, in described mixed olefins and alkane catalytic pyrolysis unit, the logistics 3 of described carbon four above cuts is converted at least in part and is rich in propylene, the catalytically cracked gas logistics 4 of ethene, with logistics 4 coolings and through separating, obtain the logistics of carbon three following cuts, its logistics 2 with carbon three following cuts is sent in the separate part of steam cracking device, with the propylene of raising steam cracking device and the output of ethene; The temperature of reaction of described olefins by catalytic cracking unit is 400～600 ℃, and reaction pressure is 0.07～0.50MPa, and volume space velocity is 0.5～100h during reaction solution
-1, the charging mass ratio of water vapour and catalytic pyrolysis raw material is 0～10; The temperature of reaction of described mixed olefins and alkane catalytic pyrolysis unit is 450～650 ℃, and reaction pressure is 0.07～0.50MPa, and volume space velocity is 0.5～100h during reaction solution
-1, the charging mass ratio of water vapour and catalytic pyrolysis raw material is 0～10;
(2) separate: with catalytically cracked gas cooling and the separation that step (1) obtains, each logistics that separates is sent into the appropriate location of the separation of steam cracking, with the propylene of raising steam cracking device and the output of ethene.
2. the method for propylene enhancing as claimed in claim 1 and ethene, it is characterized in that, after described catalytically cracked gas logistics 1 cooling, be separated into first the logistics of carbon five following cuts and the logistics of carbon six above cuts, then the logistics of carbon five following cuts is separated into logistics 2 and carbon four carbon five mixed fraction of carbon three following cuts, the logistics with carbon six above cuts mixes to enter described mixed olefins and alkane catalytic pyrolysis unit with carbon four carbon five mixed fraction again; After described catalytically cracked gas logistics 4 coolings, be separated into first the logistics of carbon six above cuts and the logistics of carbon five following cuts, then the logistics of carbon five following cuts isolated the logistics of carbon three following cuts.
3. the method for propylene enhancing as claimed in claim 1 and ethene is characterized in that, described catalytic pyrolysis system produces and the logistics of isolated carbon three following cuts is sent in the splitting gas of oil scrubber, water wash column or compressor of steam cracking separation system.
4. the method for propylene enhancing as claimed in claim 1 and ethene is characterized in that, described catalytic pyrolysis system produce and isolated C-4-fraction recycle or deliver to liquefied petroleum gas (LPG) or the torch pipeline in.
5. the method for propylene enhancing as claimed in claim 1 and ethene is characterized in that, described catalytic pyrolysis system produces and the logistics recycle of isolated carbon five above cuts or deliver to the pyrolysis gasoline hydrogenation device.
6. the method for propylene enhancing as claimed in claim 1 and ethene is characterized in that, it is 0～100 ℃ that catalytically cracked gas cools off with the temperature range of separating.
7. the method for propylene enhancing as claimed in claim 1 and ethene is characterized in that, it is 0～40 ℃ that catalytically cracked gas cools off with the temperature range of separating.
8. the method for propylene enhancing as claimed in claim 1 and ethene, it is characterized in that, the catalyzer that described catalytic pyrolysis system uses is one or more of modification or unmodified SAPO-34, ZSM-5, ZSM-11, ZSM-23, MCM-22, MCM-49, MCM-56 and mordenite.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101033166A (en) * | 2006-03-09 | 2007-09-12 | 中国石油化工股份有限公司 | Method for preparing propylene by catalytic cracking olefin with four carbon atoms or above |
| CN101081801A (en) * | 2006-05-31 | 2007-12-05 | 中国石油化工股份有限公司 | Method for preparing small molecule alkene |
| CN101092323A (en) * | 2006-06-21 | 2007-12-26 | 中国石油化工股份有限公司 | Method for preparing olefin in lightweight by catalytic cracking olefin of containing carbon |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101033166A (en) * | 2006-03-09 | 2007-09-12 | 中国石油化工股份有限公司 | Method for preparing propylene by catalytic cracking olefin with four carbon atoms or above |
| CN101081801A (en) * | 2006-05-31 | 2007-12-05 | 中国石油化工股份有限公司 | Method for preparing small molecule alkene |
| CN101092323A (en) * | 2006-06-21 | 2007-12-26 | 中国石油化工股份有限公司 | Method for preparing olefin in lightweight by catalytic cracking olefin of containing carbon |
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