CN101857520A - Method for increasing yield of propylene and ethylene - Google Patents
Method for increasing yield of propylene and ethylene Download PDFInfo
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- CN101857520A CN101857520A CN200910081767A CN200910081767A CN101857520A CN 101857520 A CN101857520 A CN 101857520A CN 200910081767 A CN200910081767 A CN 200910081767A CN 200910081767 A CN200910081767 A CN 200910081767A CN 101857520 A CN101857520 A CN 101857520A
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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 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 constitute.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 separate purification, obtains cracking products such as ethene, propylene.
In recent years, quick growth along with domestic economy, the market requirement of 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 in state's inner propene, ethene market, fill up demand gap, China recent years has started second and third continuously and has taken turns the reconstruction and extension project of ethylene industry.Comprehensive various report, before 2010, the olefin plant of tens tame scales 80～1,200,000 tons of ethene/years will appear in China.In a foreseeable future, the imbalance between supply and demand in 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 with it crude capacity does not obtain corresponding raising, 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 bigger operation surplus.Therefore, propylene, ethylene yield become an important factor that influences the 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 to be 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.At above-mentioned situation, each big petro-chemical corporation drops into strength one after another and develops carbon four and carbon four above low value alkene alkane and produce the technology and the catalyzer of 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, the product composition of C 4 olefin and paraffins mixture catalytic pyrolysis process and the product in distribution and the steam cracking process are formed the distribution basically identical, can adopt with steam cracking process in identical separating (recoverys) system separate purification and obtain the cracking product.
In addition, the certain situation in the gasoline production process also merits attention: in the past few years, in order to protect environment, in the world wide motor spirit has been proposed higher index.Different with 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 spot of aromatic hydrocarbons.As seen, the product of catalytically cracked gasoline catalytic cracking reaction form with steam cracking process in product form basically identical, can adopt with steam cracking process in (recoverys) system that separates separate purification 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 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 product of the catalytic cracking reaction of the catalytically cracked gasoline that produces in C-4-fraction that produces in C-4-fraction that produces in the oil refining process and/or the steam cracking process and/or the oil refining process form with steam cracking process in product form the characteristics of basically identical, 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, with 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 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, the catalytically cracked gas of ethene carries out feeding after the simple separation separation (recovery) system in the steam cracking process to catalytically cracked gas then.Can be the catalytic pyrolysis system of raw material with 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 so just, to improve the output of propylene, ethene in the steam cracking process by increasing by one.
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:, described raw material is converted at least in part the catalytically cracked gas that is rich in propylene and ethene with refinery's C-4-fraction and/or cracking c_4 cut and/or catalytically cracked gasoline introducing catalytic pyrolysis system;
(2) separate: the catalytically cracked gas cooling that step (1) is obtained also separates, and the isolating appropriate location of steam cracking is sent in isolating each logistics, with the propylene that improves 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 the logistics of carbon five following cuts and the logistics of carbon six above cuts earlier, then the logistics of carbon five following cuts is separated into the 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 the logistics of carbon six above cuts and the logistics of carbon five following cuts earlier, 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, catalytically cracked gas cool off with isolating temperature range be 0～100 ℃, 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 unitary temperature of reaction of described olefins by catalytic cracking is 400～600 ℃, and reaction pressure is 0.07～0.50MPa, and volume space velocity is 0.5～100h during reaction solution
-1, water vapour and catalytic pyrolysis material feeding mass ratio are 0～10; Described mixed olefins and the unitary temperature of reaction of alkane catalytic pyrolysis are 450～650 ℃, and reaction pressure is 0.07～0.50MPa, and volume space velocity is 0.5～100h during reaction solution
-1, water vapour and catalytic pyrolysis material feeding mass ratio are 0～10.
The pyrolyzer of the present invention in existing steam cracking process process with separate (recovery) system outside, increasing by one is the catalytic pyrolysis system of raw material with 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, with C 4 olefin and paraffins mixture and/or catalytically cracked gasoline is raw material, make it partly to change into to be rich in propylene by catalytic cracking reaction, the catalytically cracked gas of ethene, and the separation of this catalytically cracked gas purification 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 oil refining process and paraffins mixture and/or the steam cracking process and paraffins mixture and/or the oil refining process in existing steam cracking process is the catalytic pyrolysis system of raw material, is to improve propylene in the existing steam cracking process, a kind of practicable method of ethylene yield.
With 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 the catalytic pyrolysis system of raw material, is made up of two class catalytic cracking reaction devices.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 charging 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 with the carbon in the catalytic pyrolysis raw material four to carbon nine alkene and all or part of catalytically cracked gases that is rich in propylene, ethene that is converted into of 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 charging 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, the catalytically cracked gasoline that adds in steam cracking process to produce 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 in the catalytic pyrolysis system of raw material, catalytic pyrolysis product in this catalytic pyrolysis system is carried out initial gross separation, and isolating product is fed the corresponding position of separation (recovery) system in the steam cracking process respectively, thereby improved propylene and ethylene yield, increased economic benefit of enterprises.
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 tons of/year ethene has 11 pyrolyzer, and wherein 6 is the light oil cracking stove, 3 heavy oit pyrolysis stoves, and 1 is the lighter hydrocarbons pyrolyzer, one is standby pyrolyzer.The light oil cracking stove is based on naphtha cracking, and the heavy oit pyrolysis stove is cracked into the master with hydrogenation tail oil, and the lighter hydrocarbons pyrolyzer is cracked into the master with cycle ethane and propane.Each pyrolyzer charging capacity sees Table 1, and ethene, propylene, butane butylene yield and output see Table 2.
1,000,000 tons of olefin plant cracking stock years of table 1 are thrown oil mass
| Raw material | Petroleum naphtha | ??HVGO | Cycle ethane | Recycled propane |
| Charging capacity, ten thousand tons/year | ??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 tons/year | Total recovery, wt% | |
| Ethene | ??100.262 | ??30.97 |
| Propylene | ??50.722 | ??15.67 |
| Butane | ??0.637 | ??0.20 |
| Ultimate production, ten thousand tons/year | Total recovery, wt% | |
| 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 separation system separate purify 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, increasing by one is the catalytic pyrolysis system of raw material with C 4 olefin in the steam cracking process and paraffins mixture, this catalytic pyrolysis system mainly is made up 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 fed in catalytic cracking reaction device 1 (the 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 catalyst, 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 small amount of carbon five.
(3) separate in the rectifying tower 1 that logistics 2 is fed in this catalytic pyrolysis system, 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 fed in catalytic cracking reaction device 2 (mixed olefins and the alkane catalytic cracking reaction devices).In catalytic cracking reaction device 2, logistics 6 contacts with alkane cracking catalyst with mixed olefins and is to carry out catalytic cracking reaction under 3 hours-1 the condition in 700 ℃ of temperature of reaction, reaction pressure (gauge pressure) 0.10Mpa, air speed, 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, and 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 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 fed the pyrolysis gasoline hydrogenation device.
(11) logistics 12 is fed 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, feed in separation (recovery) system of steam cracking process in the splitting gas pipeline in the oil scrubber.
Calculation result shows, after increasing the catalytic pyrolysis system that a C 4 olefin that produces in steam cracking process and paraffins mixture be raw material, full factory ethene total recovery is 31.66%, and the propylene total recovery is 17.87%.As previously mentioned, adopt original steam of being made up of pyrolyzer and separation system to separate technology, full factory ethene total recovery is 30.97%, and full factory propylene total recovery is 15.67%.And after increasing the technology of being made up 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, increasing by one is the catalytic pyrolysis system of raw material (the raw material composition sees Table 2) with the catalytically cracked gasoline, the amount of finish of the pressure gasoline of this catalytic pyrolysis system is 50,000 tons/year, and this catalytic pyrolysis system is made of two catalytic cracking reaction devices, and is specific as follows:
Table 2, catalytically cracked gasoline are formed
(1) earlier catalytically cracked gasoline is fed in the catalytic cracking reaction device 1, the alkene of this catalytically cracked gasoline and specific catalyst 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 catalyst, 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 to be rich in the logistics 1 of propylene, ethene with the alkene part catalytic pyrolysis in the charging, 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 formation logistics 6 with logistics 3, in the catalytic cracking reaction device 2 in the logistics 6 feeding catalytic pyrolysis systems.
(4) in catalytic cracking reaction device 2, logistics 6 contacts with specific catalyst 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.In temperature of reaction is that 700 ℃, reaction pressure (gauge pressure) 0.1Mpa, water-oil ratio are 0.5, air speed is 5 hours
-1Under the condition, catalyzer 2 generates the logistics 7 that is rich in propylene, ethene with the 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) separate formation logistics 10 and logistics 11 in the rectifying tower 2 that logistics 8 is fed in this catalytic pyrolysis system, logistics 10 is carbon three following components, and logistics 11 is carbon four carbon five components.
(7) separate formation logistics 12 and logistics 13 in the rectifying tower 3 that logistics 11 is fed in the catalytic pyrolysis system, 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, feed 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 fed 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 the following components of carbon three are fed 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, increase is the catalytic pyrolysis system of raw material with 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 heat cracking technology and paraffins mixture and/or the oil refining process, under the situation that increases a small amount of catalytic cracking reaction device, full factory's ethene and productivity of propylene are significantly improved, and help enterprise and increase economic efficiency.
Claims (10)
1. the method for 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:, described raw material is converted at least in part the catalytically cracked gas that is rich in propylene and ethene with refinery's C-4-fraction and/or cracking c_4 cut and/or catalytically cracked gasoline introducing catalytic pyrolysis system;
(2) separate: the catalytically cracked gas cooling that step (1) is obtained also separates, and the isolating appropriate location of steam cracking is sent in isolating each logistics, with the propylene that improves steam cracking device and the output of ethene.
2. the method for propylene enhancing as claimed in claim 1 and ethene is characterized in that, described catalytic pyrolysis system comprises olefins by catalytic cracking unit, mixed olefins and alkane catalytic pyrolysis unit and separating unit.
3. the method for propylene enhancing as claimed in claim 2 and ethene, it is characterized in that, 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.
4. the method for propylene enhancing as claimed in claim 3 and ethene, it is characterized in that, after described catalytically cracked gas logistics 1 cooling, be separated into the logistics of carbon five following cuts and the logistics of carbon six above cuts earlier, then the logistics of carbon five following cuts is separated into the 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 the logistics of carbon six above cuts and the logistics of carbon five following cuts earlier, then the logistics of carbon five following cuts isolated the logistics of carbon three following cuts.
5. the method for propylene enhancing as claimed in claim 3 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.
6. the method for propylene enhancing as claimed in claim 3 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.
7. the method for propylene enhancing as claimed in claim 3 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.
8. the method for propylene enhancing as claimed in claim 3 and ethene is characterized in that, catalytically cracked gas cool off with isolating temperature range be 0～100 ℃, preferred 0～40 ℃.
9. 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.
10. the method for propylene enhancing as claimed in claim 3 and ethene is characterized in that, the unitary temperature of reaction of described olefins by catalytic cracking is 400～600 ℃, and reaction pressure is 0.07～0.50MPa, and volume space velocity is 0.5～100h during reaction solution
-1, water vapour and catalytic pyrolysis material feeding mass ratio are 0～10; Described mixed olefins and the unitary temperature of reaction of alkane catalytic pyrolysis are 450～650 ℃, and reaction pressure is 0.07～0.50MPa, and volume space velocity is 0.5～100h during reaction solution
-1, water vapour and catalytic pyrolysis material feeding mass ratio are 0～10.
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| CN103086826A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Method for simultaneously producing ethylene and propylene |
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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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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086826A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Method for simultaneously producing ethylene and propylene |
| CN103086826B (en) * | 2011-10-28 | 2015-09-16 | 中国石油化工股份有限公司 | The co-production of a kind of ethene and propylene |
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