CN102286292A - Method for increase production of propylene and ethylene by pyrolyzing C4 raffinate - Google Patents

Method for increase production of propylene and ethylene by pyrolyzing C4 raffinate Download PDF

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CN102286292A
CN102286292A CN2010102044006A CN201010204400A CN102286292A CN 102286292 A CN102286292 A CN 102286292A CN 2010102044006 A CN2010102044006 A CN 2010102044006A CN 201010204400 A CN201010204400 A CN 201010204400A CN 102286292 A CN102286292 A CN 102286292A
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logistics
carbon
propylene
catalytic pyrolysis
ethene
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CN102286292B (en
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刘小波
付啸
郝雪松
周丛
白杰
王国清
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

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Abstract

The invention relates to a method, which takes a C4 alkane-alkene mixture produced by a steam pyrolyzing process for preparing ethylene as a raw material, and is used for improving the production volume of propylene and ethylene prepared by a device for preparing ethylene by a steam pyrolyzing process, in particular to a method for the increase production of propylene and ethylene by pyrolyzing C4 raffinate. The method comprises the following steps of: adding a treatment system for pyrolyzing C4-fraction in the existing steam pyrolyzing device; fully converting a pyrolytic C4 alkane-alkene mixture into catalytic pyrolysis gas with rich propylene and ethylene by the steps of C4 alkene-akane catalytic pyrolysis, alkene and alkane mixed catalytic pyrolysis, C4 alkane catalytic pyrolysis, and the like; simply separating the catalytic pyrolysis gas; and introducing the gas into a separation (recovery) system in the steam pyrolyzing process to further separation and purification so as to effectively improve the production volume of the propylene and ethylene in the steam pyrolyzing process. In the invention, as only three catalytic pyrolysis reactors and simple separation equipment are added, the potential of the separation (recovery) system in the steam pyrolyzing device can be utilized, and the production volume of the propylene and ethylene can be increased. The method can be used for the existing steam pyrolyzing device, and can increase the economic benefit of enterprises.

Description

Utilize the method for cracking c_4 raffinate propylene enhancing and ethene
Technical field
The present invention relates to the method for a kind of propylene enhancing and ethene, more particularly, the present invention relates to a kind of cracking c_4 raffinate that utilizes steam cracking device to produce and be raw material, the method for propylene enhancing, ethene.
Background technology
Low-carbon alkene such as propylene, ethene is an important chemical material.Propylene is mainly derived from the FCC apparatus and the ethylene unit of refinery, both account for 32% and 66% of propone output respectively, ethene mainly is that the tube furnace steam cracking by petroleum naphtha obtains, and the production of propylene generally all is the byproduct as ethylene production, mainly obtains by steam cracking and catalytic cracking system ethylene unit.But the propylene as the byproduct form obtains can not satisfy its demand far away at present.Therefore develop the technology of the production propylene of many hearts, mainly contained Technologies such as dehydrogenating propane, low-carbon alkene disproportionation, low-carbon alkene cracking, preparing propylene from methanol at present.Low-carbon alkene cracking system propylene technology not only can be used for producing propylene, ethene, and can improve the added value of low-carbon alkene, has very big development prospect.
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.And C 4 mixture obtains the cracking c_4 raffinate through the divinyl extracting, and wherein butene content can reach 95.9%, and butane content only is 4.1%.For this part C 4 olefin and paraffins mixture, except that as practicing factory's fuel, often to use as city domestic fuel liquefied petroleum gas (LPG), economic worth is relatively low, and how better utilised plays this part carbon four has caused extensive concern day by day.
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.
The present invention promptly is to provide a kind of method of utilizing cracking c_4 raffinate propylene enhancing, ethene.
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, proposed to increase in existing steam cracking device to the treatment system of cracking C-4-fraction to increase the method for propylene and ethylene yield in the whole cracking flow process.
Method provided by the invention, by in existing steam cracking device, increasing the treatment system of a cracking c_4 cut, in conjunction with steam cracking device and olefins by catalytic cracking, the advantage of technologies such as alkane catalytic pyrolysis, utilize the C _ 4 alkene catalytic pyrolysis that carries out successively, steps such as mixed olefins and alkane catalytic pyrolysis and butane catalytic pyrolysis, cracking c_4 alkene and paraffins mixture are fully transformed the catalytically cracked gas that propylene and ethene are rich in generation, then catalytically cracked gas is carried out feeding after the simple separation separation (recoverys) system in the steam cracking process so that further separation and purification treatment, thereby improve the output of propylene and ethene in the steam cracking process effectively.
Concrete technical scheme is as follows:
The method of utilizing cracking c_4 raffinate propylene enhancing and ethene of the present invention, in steam cracking and tripping device thereof, increase the treatment system of a cracking c_4 cut, the treatment system of described cracking c_4 cut comprises C _ 4 alkene catalytic pyrolysis unit, mixed olefins and alkane catalytic pyrolysis unit and butane catalytic pyrolysis unit, said method comprising the steps of:
(1) C _ 4 alkene catalytic pyrolysis: the cracking c_4 raffinate is introduced the C _ 4 alkene catalytic pyrolysis unit, described raw material is converted into the catalytically cracked gas that is rich in propylene and ethene at least in part, be separated into carbon three following cuts and carbon four above cuts;
(2) mixed olefins and alkane catalytic pyrolysis: the carbon four above cuts that step (1) is obtained are converted into the catalytically cracked gas that is rich in propylene and ethene at least in part in mixed olefins and alkane catalytic pyrolysis unit, are separated into carbon three following cuts and carbon four above cuts;
(3) butane catalytic pyrolysis: the carbon four above cuts that step (2) obtains are sent into butane catalytic pyrolysis unit, make it be converted into the catalytically cracked gas that is rich in propylene and ethene at least in part, be separated into carbon three following cuts and carbon four above cuts;
(4) product reclaims: the carbon three following cuts that step (1), step (2) and step (3) are obtained are respectively sent in the splitting gas of oil scrubber, water wash column or compressor of steam cracking and tripping device thereof, with the propylene of raising steam cracking device and the output of ethene together.
Preferably, in described C _ 4 alkene catalytic pyrolysis unit, alkene in the described cracking c_4 raffinate is converted into the catalytically cracked gas logistics 1 that is rich in propylene and ethene at least in part, with logistics 1 cooling and separation, 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, make the logistics 3 of described carbon four above cuts be converted into the catalytically cracked gas logistics 4 that is rich in propylene and ethene at least in part, with logistics 4 coolings and through separating, obtain the logistics 5 of carbon three following cuts and the logistics 6 of carbon four above cuts, described butane catalytic pyrolysis unit is introduced in the logistics 6 of carbon four above cuts, in described butane catalytic pyrolysis unit, the logistics 6 of described carbon four above cuts is converted into the catalytically cracked gas logistics 7 that is rich in propylene and ethene at least in part, with logistics 7 coolings and separation, obtain the logistics 8 of carbon three following cuts and the logistics 9 of carbon four above cuts, logistics 8 with carbon three following cuts, logistics 5 is sent in the separation system of steam cracking device with logistics 2, with the propylene of raising steam cracking device and the output of ethene.
Preferably, in described C _ 4 alkene catalytic pyrolysis unit, alkene in the described cracking c_4 raffinate is converted into the catalytically cracked gas logistics 1 that is rich in propylene and ethene at least in part, with logistics 1 cooling and separation, 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, make the logistics 3 of described carbon four above cuts be converted into the catalytically cracked gas logistics 4 that is rich in propylene and ethene at least in part, be separated into the logistics of carbon six above cuts and the logistics of carbon five following cuts earlier after logistics 4 coolings, then the logistics of carbon five following cuts is isolated the logistics 5 and the logistics 6 that contains the C-4-fraction of small amount of carbon five of carbon three following cuts, logistics 6 is fed described butane catalytic pyrolysis unit, the catalytically cracked gas logistics 7 that logistics 6 is converted at least in part be rich in propylene and ethene, with logistics 7 coolings and separation, obtain the logistics 8 of the cut of carbon below three and the logistics 9 of carbon four above cuts, logistics 8 with carbon three following cuts, logistics 5 is sent in the separation system of steam cracking device with logistics 2, with the propylene of raising steam cracking device and the output of ethene.
Preferably, with the C-4-fraction recycle in the logistics 9 of described carbon four above cuts send into liquefied petroleum gas (LPG) or the torch pipeline in.
Preferably, with the five above cut recycles of the carbon in the logistics 9 of described carbon four above cuts or send into the pyrolysis gasoline hydrogenation device.
Preferably, catalytically cracked gas cool off with isolating temperature range be 0～100 ℃, preferred 0～40 ℃.
Preferably, described C _ 4 alkene catalytic pyrolysis unit, the catalyzer that butane catalytic pyrolysis unit and mixed olefins and alkane catalytic pyrolysis unit use is modification or unmodified SAPO-34, ZSM-5, ZSM-11, ZSM-23, MCM-22, MCM-49, one or more of MCM-56 and mordenite, modifying element comprises phosphorus, lanthanum, cerium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, cadmium, zirconium, molybdenum, in tungsten or the aluminium one or more, used metal-salt is the carbonate of above-mentioned selected metal during modification, vitriol, nitrate, oxalate, phosphoric acid salt, muriate or corresponding ammonium salt.
Preferably, the temperature of reaction of described C _ 4 alkene catalytic pyrolysis is 400～600 ℃, and reaction pressure is 0.07～0.50MPa, and volume space velocity is 0.5～100h during liquid -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 liquid -1, the charging mass ratio of water vapour and butane and alkene mixture is 0～10; The unitary temperature of reaction of described butane catalytic pyrolysis is 400～700 ℃, and reaction pressure (gauge pressure) scope is 0.01～0.20MPa, and the gas phase air speed is 2000～4000h -1
Preferably, described cracking c_4 raffinate is removed wherein alkynes and divinyl by selective hydrogenation earlier, sends into described cracking c_4 cut treatment system again.
The pyrolyzer of the present invention in existing steam cracking process process with separate (recovery) system outside, only need to increase by one by the C _ 4 alkene catalytic pyrolysis unit, the cracking c_4 treatment system that butane catalytic pyrolysis unit and mixed olefins and alkane catalytic pyrolysis unit are formed, make butane and alkene mixture change propylene into to greatest extent, the split product of ethene and other by products, and these split products are through after the simple refrigerated separation, the separation system that is admitted to steam cracking device is separated purification, having made full use of the operation surplus of existing separation system, is to improve propylene in the existing steam cracking process, a kind of practicable method of ethylene yield.
The cracking c_4 treatment system that is raw material with the C 4 olefin that produces in the steam cracking process and paraffins mixture, form by three class catalytic cracking reaction devices, comprise C _ 4 alkene catalytic pyrolysis reactor, butane catalytic cracking reaction device and mixed olefins and alkane catalytic cracking reaction device.These catalytic cracking reaction devices can be one or more combinations in fixed bed, moving-bed, the fluidized-bed.
The catalyzer that uses in C _ 4 alkene catalytic pyrolysis reactor, butane catalytic cracking reaction device and mixed olefins and the alkane catalytic cracking reaction device 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.Modifying element comprises one or more in phosphorus, lanthanum, cerium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, cadmium, zirconium, molybdenum, tungsten or the aluminium, used metal-salt is carbonate, vitriol, nitrate, oxalate, phosphoric acid salt or the muriate of above-mentioned selected metal during modification, also can be corresponding ammonium salt etc.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.
The C _ 4 alkene catalytic pyrolysis catalyzer can be converted into the C 4 olefin in the cracking c_4 raw material catalytically cracked gas of propylene and ethene at least in part.C _ 4 alkene catalytic pyrolysis catalyst reactor range of reaction temperature is 400～600 ℃, and reaction pressure (gauge pressure) scope is 0.07～0.50MPa, and water and hydrocarbon raw material part by weight are 0～10, and material charging air speed scope is 0.5～100h -1
Mixed olefins and alkane catalytic cracking catalyst can with the carbon five that from carbon four cracking unit, produces or more the olefin fraction of high carbon atom number be converted into the catalytically cracked gas that is rich in propylene and ethene at least in part.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 liquid -1, the charging mass ratio of water vapour and butane and alkene mixture is 0～10.
The butane catalytic cracking catalyst can be with all or part of catalytically cracked gas that is rich in propylene and ethene that is converted into of the butane in the catalytic pyrolysis raw material.This catalyst reaction temperatures scope is 400～700 ℃, and reaction pressure (gauge pressure) scope is 0.01～0.20MPa, and the gas phase air speed is 2000～4000h -1
The used raw material of cracking c_4 treatment system of the present invention is the C-4-fraction of drawing from the separation system of steam cracking device, and this raw material has been removed most divinyl in butadiene extraction unit.Preferably, this raw material before sending into the cracking c_4 treatment system, earlier by selective hydrogenation device removed wherein alkynes and the divinyl extracting after remaining few butadiene.
Mentioned catalyzer all can adopt existing catalyst preparation technology preparation among the present invention, and the Beijing Chemical Research Institute can produce described catalyzer.
In sum, in steam cracking process, add the cracking c_4 treatment system that is raw material with the C 4 olefin that produces in the steam cracking device and paraffins mixture, the product that this system is obtained carries out initial gross separation, and the product after will separating feeds 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 1,000,000 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
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
Adopt method of the present invention, on the basis of comparative example 1, increase the cracking c_4 treatment system to improve the output of propylene and ethene.That this system produces with steam cracking device and be raw material through butane and alkene mixture after divinyl extracting and the selective hydrogenation, comprise C _ 4 alkene catalytic pyrolysis unit, higher olefins catalytic pyrolysis unit, butane catalytic pyrolysis unit and separating unit.Concrete grammar is as follows:
(1) at first C 4 olefin in the comparative example 1 and paraffins mixture raw material are sent into the C _ 4 alkene catalytic pyrolysis unit, catalytic cracking reaction takes place in the C 4 olefin in the raw material under the effect of catalyzer, temperature of reaction is that 520 ℃, reaction pressure (gauge pressure) are 3h for 0.20MPa, air speed -170% C 4 olefin generation catalytic cracking reaction generates low-carbon alkene and other hydro carbons by products such as propylene, ethene, and raw material changes the logistics 1 that is rich in propylene, ethene into, and wherein propylene content is 30.7wt%, and ethylene content is 9.6wt%.The catalyzer that the C _ 4 alkene catalytic pyrolysis unit adopts is the ZSM-5 molecular sieve type catalyst of modification, it consists of: (silica alumina ratio is 100 for phosphorus 3wt%, lanthanum 1wt%, ZSM-5 molecular sieve 70wt%, particle diameter is 500nm), silicon oxide 26wt%, produce by the Beijing Chemical Research Institute.
(2) logistics 1 is cooled to 20 ℃ of separation, obtains logistics 2 and logistics 3, wherein logistics 2 is carbon five following cuts, and logistics 3 is for containing the carbon six above cuts 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 above cuts.
(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 7.56wt%;
2) unreacted C 4 olefin, its content are 52.47wt%;
3) content be 25.25wt% 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 11.80wt%;
5) aromatic hydrocarbons, its content are 1wt%.
(5) logistics 6 is fed mixed olefins and alkane catalytic pyrolysis unit, temperature of reaction is 600 ℃, and reaction pressure is 0.15MPa, and volume space velocity is 5h during liquid -1, the charging mass ratio of water vapour and butane and alkene mixture is 1.In this reaction member, most carbon four above alkene and a small amount of alkane generation catalytic cracking reaction generate the logistics 7 that is rich in propylene and ethene, and wherein propylene content is 23.7wt%, and ethylene content is 7.4wt%.The catalyzer that mixed olefins and alkane catalytic pyrolysis unit adopt is the ZSM-5 molecular sieve type catalyst of modification, and it consists of: phosphorus 3wt%, ZSM-5 molecular sieve 65wt% (silica alumina ratio is 30), silicon oxide 32wt%, produced by the Beijing Chemical Research Institute.
(5) logistics 7 is cooled to 20 ℃ of separation, obtains logistics 8, logistics 9, logistics 8 is carbon five following cuts, and logistics 9 is for containing the carbon six above cuts of small amount of carbon five.
(6) with separating in the logistics 8 feeding rectifying tower 2, obtain logistics 10 and logistics 11, logistics 10 is carbon three following cuts, and logistics 11 is carbon four carbon five mixed fraction, and logistics 11 and logistics 9 are mixed the logistics 12 that obtains carbon four above cuts.
(7) cut 12 is fed butane catalytic pyrolysis unit, temperature of reaction is that 650 ℃, reaction pressure (gauge pressure) are 3000h for 0.10MPa, volume space velocity -1In this reaction member, 80% alkane generation catalytic cracking reaction generates the logistics 13 that is rich in propylene, ethene, and wherein propylene content is 22.7wt%, and ethylene content is 35.6wt%.The catalyzer that butane catalytic pyrolysis unit adopts is the ZSM-5 molecular sieve type catalyst of modification, and it consists of: chromium 2wt%, ZSM-5 molecular sieve 98wt% (silica alumina ratio is 30), produced by the Beijing Chemical Research Institute.
(8) logistics 13 is cooled to 20 ℃, obtains logistics 14 and logistics 15, logistics 14 is carbon five following cuts, and logistics 15 is the carbon six above cuts of small amount of carbon five.
(9) with separating in the logistics 14 feeding rectifying tower 3, obtain logistics 16 and logistics 17, logistics 16 is carbon three following cuts, and logistics 17 is for containing carbon four mixed fraction of small amount of carbon five.
(10) logistics 4, logistics 10, logistics 16 are mixed in the splitting gas of the oil scrubber, water wash column or the compressor that feed the steam cracking device separation system, with the propylene of raising steam cracking device and the output of ethene.
(11) logistics 9 is sent into the pyrolysis gasoline hydrogenation device of steam cracking device separation system.
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 32.18%, and the propylene total recovery is 18.19%.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 1.21%, and the propylene total recovery increases by 2.52%.
Embodiment 2
Adopt method of the present invention, on the basis of comparative example 1, increase the cracking c_4 treatment system to improve the output of propylene and ethene.That this system produces with steam cracking device and be raw material through butane and alkene mixture after divinyl extracting and the selective hydrogenation, comprise C _ 4 alkene catalytic pyrolysis unit, higher olefins catalytic pyrolysis unit, butane catalytic pyrolysis unit and separating unit.Concrete grammar is as follows:
(1) with the C 4 olefin in the comparative example 1 and paraffins mixture raw material after shortening is removed wherein a spot of divinyl, send into the C _ 4 alkene catalytic pyrolysis unit, catalytic cracking reaction takes place in the C 4 olefin in the raw material under the effect of catalyzer, temperature of reaction is that 520 ℃, reaction pressure (gauge pressure) are 3h for 0.20MPa, air speed -170% C 4 olefin generation catalytic cracking reaction generates low-carbon alkene and other hydro carbons by products such as propylene, ethene, and raw material changes the logistics 1 that is rich in propylene, ethene into, and wherein propylene content is 30.7wt%, and ethylene content is 9.6wt%.The catalyzer that the C _ 4 alkene catalytic pyrolysis unit adopts is the ZSM-5 molecular sieve type catalyst of modification, it consists of: (silica alumina ratio is 100 for phosphorus 3wt%, lanthanum 1wt%, ZSM-5 molecular sieve 70wt%, particle diameter is 500nm), silicon oxide 26wt%, produce by the Beijing Chemical Research Institute.
(2) logistics 1 is cooled to 20 ℃ of separation, obtains logistics 2 and logistics 3, wherein logistics 2 is carbon five following cuts, and logistics 3 is for containing the carbon six above cuts 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 above cuts.
(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 7.56wt%;
2) unreacted C 4 olefin, its content are 52.47wt%;
3) content be 25.25wt% 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 11.80wt%;
5) aromatic hydrocarbons, its content are 1wt%.
(5) logistics 6 is fed mixed olefins and alkane catalytic pyrolysis unit, temperature of reaction is 600 ℃, and reaction pressure is 0.15MPa, and volume space velocity is 5h during liquid -1, the charging mass ratio of water vapour and butane and alkene mixture is 1.In this reaction member, most carbon four above alkene and a small amount of alkane generation catalytic cracking reaction generate the logistics 7 that is rich in propylene and ethene, and wherein propylene content is 23.7wt%, and ethylene content is 7.4wt%.The catalyzer that mixed olefins and alkane catalytic pyrolysis unit adopt is the ZSM-5 molecular sieve type catalyst of modification, and it consists of: phosphorus 3wt%, ZSM-5 molecular sieve 65wt% (silica alumina ratio is 30), silicon oxide 32wt%, produced by the Beijing Chemical Research Institute.
(5) logistics 7 is cooled to 20 ℃ of separation, obtains logistics 8, logistics 9, logistics 8 is carbon five following cuts, and logistics 9 is for containing the carbon six above cuts of small amount of carbon five.
(6) with separating in the logistics 8 feeding rectifying tower 2, obtain logistics 10 and logistics 11, logistics 10 is carbon three following cuts, and logistics 11 is for containing carbon four mixed fraction of 20wt% carbon five.
(7) cut 11 is fed butane catalytic pyrolysis unit, temperature of reaction is that 650 ℃, reaction pressure (gauge pressure) are 3000h for 0.10MPa, volume space velocity -1In this reaction member, 80% alkane generation catalytic cracking reaction generates the logistics 12 that is rich in propylene, ethene, and wherein propylene content is 19.8wt%, and ethylene content is 23.8wt%.The catalyzer that butane catalytic pyrolysis unit adopts is the ZSM-5 molecular sieve type catalyst of modification, and it consists of: chromium 2wt%, ZSM-5 molecular sieve 98wt% (silica alumina ratio is 30), produced by the Beijing Chemical Research Institute.
(8) logistics 12 is cooled to 20 ℃, obtains logistics 13 and logistics 14, logistics 13 is carbon five following cuts, and logistics 14 is for containing the carbon six above cuts of small amount of carbon five.
(9) with separating in the logistics 13 feeding rectifying tower 3, obtain logistics 15 and logistics 16, logistics 15 is carbon three following cuts, and logistics 16 is for containing carbon four mixed fraction of small amount of carbon five.
(10) logistics 4, logistics 10, logistics 15 are mixed in the splitting gas of the oil scrubber, water wash column or the compressor that feed the steam cracking device separation system, with the propylene of raising steam cracking device and the output of ethene.
(11) logistics 9 is sent into the pyrolysis gasoline hydrogenation device of steam cracking device separation system.
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 31.70%, and the propylene total recovery is 17.90%.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 0.73%, and the propylene total recovery increases by 2.23%.
This shows, in original steam cracking process process, the cracking c_4 treatment system that increase is raw material with the C 4 olefin that produces in the steam heat cracking technology and paraffins mixture, under the situation that increases a small amount of catalytic cracking reaction device, the split product that makes full use of the ethylene plant reclaims separation system, product cut to volume increase reclaims, and full factory ethene and productivity of propylene are improved significantly, and helps enterprise and increases economic efficiency.

Claims (10)

1. method of utilizing cracking c_4 raffinate propylene enhancing and ethene, it is characterized in that, in steam cracking and tripping device thereof, increase a cracking c_4 cut treatment system, the treatment system of described cracking c_4 cut comprises C _ 4 alkene catalytic pyrolysis unit, mixed olefins and alkane catalytic pyrolysis unit and butane catalytic pyrolysis unit, said method comprising the steps of:
(1) C _ 4 alkene catalytic pyrolysis: the cracking c_4 raffinate is introduced the C _ 4 alkene catalytic pyrolysis unit, described raw material is converted into the catalytically cracked gas that is rich in propylene and ethene at least in part, be separated into carbon three following cuts and carbon four above cuts;
(2) mixed olefins and alkane catalytic pyrolysis: the carbon four above cuts that step (1) is obtained are converted into the catalytically cracked gas that is rich in propylene and ethene at least in part in mixed olefins and alkane catalytic pyrolysis unit, are separated into carbon three following cuts and carbon four above cuts;
(3) butane catalytic pyrolysis: the carbon four above cuts that step (2) obtains are sent into butane catalytic pyrolysis unit, make it be converted into the catalytically cracked gas that is rich in propylene and ethene at least in part, be separated into carbon three following cuts and carbon four above cuts;
(4) product reclaims: the carbon three following cuts that step (1), step (2) and step (3) are obtained are respectively sent in the splitting gas of oil scrubber, water wash column or compressor of steam cracking and tripping device thereof, with the propylene of raising steam cracking device and the output of ethene together.
2. the method for utilizing cracking c_4 raffinate propylene enhancing and ethene as claimed in claim 1, it is characterized in that, in described C _ 4 alkene catalytic pyrolysis unit, alkene in the described cracking c_4 raffinate is converted into the catalytically cracked gas logistics 1 that is rich in propylene and ethene at least in part, with logistics 1 cooling and separation, 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, make the logistics 3 of described carbon four above cuts be converted into the catalytically cracked gas logistics 4 that is rich in propylene and ethene at least in part, with logistics 4 coolings and through separating, obtain the logistics 5 of carbon three following cuts and the logistics 6 of carbon four above cuts, described butane catalytic pyrolysis unit is introduced in the logistics 6 of carbon four above cuts, in described butane catalytic pyrolysis unit, the logistics 6 of described carbon four above cuts is converted into the catalytically cracked gas logistics 7 that is rich in propylene and ethene at least in part, with logistics 7 coolings and separation, obtain the logistics 8 of the cut of carbon below three and the logistics 9 of carbon four above cuts, logistics 8 with carbon three following cuts, logistics 5 is sent in the separation system of steam cracking device with logistics 2, with the propylene of raising steam cracking device and the output of ethene.
3. the method for utilizing cracking c_4 raffinate propylene enhancing and ethene as claimed in claim 1, it is characterized in that, in described C _ 4 alkene catalytic pyrolysis unit, alkene in the described cracking c_4 raffinate is converted into the catalytically cracked gas logistics 1 that is rich in propylene and ethene at least in part, with logistics 1 cooling and separation, 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, make the logistics 3 of described carbon four above cuts be converted into the catalytically cracked gas logistics 4 that is rich in propylene and ethene at least in part, be separated into the logistics of carbon six above cuts and the logistics of carbon five following cuts earlier after logistics 4 coolings, then the logistics of carbon five following cuts is isolated the logistics 5 and the logistics 6 that contains the C-4-fraction of small amount of carbon five of carbon three following cuts, logistics 6 is fed described butane catalytic pyrolysis unit, the catalytically cracked gas logistics 7 that logistics 6 is converted at least in part be rich in propylene and ethene, with logistics 7 coolings and separation, obtain the logistics 8 of carbon three following cuts and the logistics 9 of carbon four above cuts, logistics 8 with carbon three following cuts, logistics 5 is sent in the separation system of steam cracking device with logistics 2, with the propylene of raising steam cracking device and the output of ethene.
4. as claim 2 or the 3 described methods of utilizing cracking c_4 raffinate propylene enhancing and ethene, it is characterized in that, with the C-4-fraction recycle in the logistics 9 of described carbon four above cuts send into liquefied petroleum gas (LPG) or the torch pipeline in.
5. as claim 2 or the 3 described methods of utilizing cracking c_4 raffinate propylene enhancing and ethene, it is characterized in that, with the five above cut recycles of the carbon in the logistics 9 of described carbon four above cuts or send into the pyrolysis gasoline hydrogenation device.
6. as claim 2 or the 3 described methods of utilizing cracking c_4 raffinate propylene enhancing and ethene, it is characterized in that, catalytically cracked gas cool off with isolating temperature range be 0～100 ℃.
7. as claim 2 or the 3 described methods of utilizing cracking c_4 raffinate propylene enhancing and ethene, it is characterized in that, catalytically cracked gas cool off with isolating temperature range be 0～40 ℃.
8. as claim 2 or the 3 described methods of utilizing cracking c_4 raffinate propylene enhancing and ethene, it is characterized in that, described C _ 4 alkene catalytic pyrolysis unit, the catalyzer that butane catalytic pyrolysis unit and mixed olefins and alkane catalytic pyrolysis unit use is modification or unmodified SAPO-34, ZSM-5, ZSM-11, ZSM-23, MCM-22, MCM-49, one or more of MCM-56 and mordenite, modifying element comprises phosphorus, lanthanum, cerium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, cadmium, zirconium, molybdenum, in tungsten or the aluminium one or more, used metal-salt is the carbonate of above-mentioned selected metal during modification, vitriol, nitrate, oxalate, phosphoric acid salt, muriate or corresponding ammonium salt.
9. as claim 2 or the 3 described methods of utilizing cracking c_4 raffinate propylene enhancing and ethene, it is characterized in that, the temperature of reaction of described C _ 4 alkene catalytic pyrolysis is 400～600 ℃, and reaction pressure is 0.07～0.50MPa, and volume space velocity is 0.5～100h during liquid -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 liquid -1, the charging mass ratio of water vapour and butane and alkene mixture is 0～10; The unitary temperature of reaction of described butane catalytic pyrolysis is 400～700 ℃, and reaction pressure (gauge pressure) scope is 0.01～0.20MPa, and the gas phase air speed is 2000～4000h -1
10. the method for utilizing cracking c_4 raffinate propylene enhancing and ethene as claimed in claim 1, it is characterized in that, described cracking c_4 raffinate is removed wherein alkynes and divinyl by selective hydrogenation earlier, sends into described cracking c_4 cut treatment system again.
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CN109422610A (en) * 2017-09-04 2019-03-05 中国石油化工股份有限公司 The method of increasing output of ethylene
CN114478175A (en) * 2020-11-13 2022-05-13 中国石化工程建设有限公司 System and method for increasing yield of low-carbon olefin
CN114931970A (en) * 2022-04-18 2022-08-23 中国石油大学(华东) Catalyst for preparing ethylene and propylene by catalytic cracking of low-carbon olefin and method thereof

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CN101734990A (en) * 2008-11-25 2010-06-16 中国石油天然气股份有限公司 Method for preparing ethylene by steam cracking of tubular cracking furnace

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CN109422610A (en) * 2017-09-04 2019-03-05 中国石油化工股份有限公司 The method of increasing output of ethylene
CN109422610B (en) * 2017-09-04 2022-08-12 中国石油化工股份有限公司 Method for increasing yield of ethylene
CN114478175A (en) * 2020-11-13 2022-05-13 中国石化工程建设有限公司 System and method for increasing yield of low-carbon olefin
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