CN102286292B - 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

Info

Publication number
CN102286292B
CN102286292B CN2010102044006A CN201010204400A CN102286292B CN 102286292 B CN102286292 B CN 102286292B CN 2010102044006 A CN2010102044006 A CN 2010102044006A CN 201010204400 A CN201010204400 A CN 201010204400A CN 102286292 B CN102286292 B CN 102286292B
Authority
CN
China
Prior art keywords
logistics
carbon
propylene
catalytic pyrolysis
ethene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN2010102044006A
Other languages
Chinese (zh)
Other versions
CN102286292A (en
Inventor
刘小波
付啸
郝雪松
周丛
白杰
王国清
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Original Assignee
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Beijing Research Institute of Chemical Industry, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Research Institute of Chemical Industry
Priority to CN2010102044006A priority Critical patent/CN102286292B/en
Publication of CN102286292A publication Critical patent/CN102286292A/en
Application granted granted Critical
Publication of CN102286292B publication Critical patent/CN102286292B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

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 a kind of method 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
The low-carbon alkene such as propylene, ethene is important industrial chemicals.Propylene is mainly derived from FCC apparatus and the ethylene unit of refinery, both account for respectively 32% and 66% of propone output, ethene is mainly that the tube furnace steam cracking by petroleum naphtha obtains, and the production of propylene is all generally the byproduct as ethylene production, mainly obtains by steam cracking and catalytic cracking ethylene unit processed.But the propylene as the byproduct form obtains can not satisfy its demand far away at present.Therefore develop the technique of the production propylene of many hearts, mainly contained at present the Technologies such as dehydrogenating propane, low-carbon alkene disproportionation, low-carbon alkene cracking, preparing propylene from methanol.Low-carbon alkene cracking propylene technology not only can be used for producing propylene, ethene, and can improve the added value of low-carbon alkene, has very large development prospect.
In the split product of steam cracking process process, except main purpose product ethene, propylene, divinyl, aromatic hydrocarbons, the C 4 olefin and the paraffins mixture that generally also contain 4～10 (weight) %, wherein about 70 (weight) % is above is butylene.And C 4 mixture obtains the cracking c_4 raffinate through Butadiene Extraction, and wherein butene content can reach 95.9%, and butane content is only 4.1%.For this part C 4 olefin and paraffins mixture, except 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.
For above-mentioned situation, each large petro-chemical corporation drops into one after another strength and develops technique and the catalyzer that carbon four and the above low value alkene of carbon four alkane are produced 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 is mainly 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 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.
The present invention namely 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 the low-carbon alkene such as state's inner propene and ethene market, proposed to increase in existing steam cracking device to the treatment system of the cracking C-4-fraction method with propylene in increasing whole cracking flow process and ethylene yield.
method provided by the invention, by increase the treatment system of a cracking c_4 cut in existing steam cracking device, in conjunction with steam cracking device and olefins by catalytic cracking, the advantage of the techniques such as alkane catalytic pyrolysis, utilize the C _ 4 alkene catalytic pyrolysis that carries out successively, the 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 passing into after simple separation separation (recovery) system in steam cracking process so that further separation and purification treatment, thereby effectively improve the output of propylene and ethene in steam cracking process.
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: with cracking c_4 raffinate introducing C _ 4 alkene catalytic pyrolysis unit, described raw material is converted at least in part the catalytically cracked gas that is rich in propylene and ethene, is separated into the following cut of carbon three and the above cut of carbon four;
(2) mixed olefins and alkane catalytic pyrolysis: make the above cut of carbon four that step (1) obtains be converted at least in part the catalytically cracked gas that is rich in propylene and ethene in mixed olefins and alkane catalytic pyrolysis unit, be separated into the following cut of carbon three and the above cut of carbon four;
(3) butane catalytic pyrolysis: the above cut of carbon four that step (2) is obtained is sent into butane catalytic pyrolysis unit, make it be converted at least in part the catalytically cracked gas that is rich in propylene and ethene, be separated into the following cut of carbon three and the above cut of carbon four;
(4) product reclaims: the following cut of carbon three that step (1), step (2) and step (3) are obtained is 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 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, cooling and the separation with logistics 1, 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 at least in part the catalytically cracked gas logistics 4 that is rich in propylene and ethene, logistics 4 is cooling 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, cooling and the separation with logistics 7, 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 together 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 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, cooling and the separation with logistics 1, 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 at least in part the catalytically cracked gas logistics 4 that is rich in propylene and ethene, the cooling rear logistics of carbon six above cuts and the logistics of carbon five following cuts of first being separated into of logistics 4, then the logistics of carbon five following cuts is isolated the logistics 5 and the logistics 6 that contains the C-4-fraction of a small amount of carbon five of carbon three following cuts, logistics 6 is passed into 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, cooling and the separation with logistics 7, 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 together 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 above cut recycle of the carbon five in the logistics 9 of described carbon four above cuts or send into the pyrolysis gasoline hydrogenation device.
Preferably, it is 0～100 ℃ that catalytically cracked gas carries out cooling temperature range with separating, preferred 0～40 ℃.
preferably, described C _ 4 alkene catalytic pyrolysis unit, the catalyzer of butane catalytic pyrolysis unit and mixed olefins and the unit use of alkane catalytic pyrolysis 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, one or more in tungsten or aluminium, during modification, metal-salt used is the carbonate of above-mentioned selected metal, 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 during liquid, volume space velocity is 0.5～100h -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 during liquid, volume space velocity is 0.5～100h -1, the charging mass ratio of water vapour and butane and alkene mixture is 0～10; The temperature of reaction of described butane catalytic pyrolysis unit 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 first removed by alkynes and divinyl that selective hydrogenation is incited somebody to action wherein, then sends into described cracking c_4 cut treatment system.
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 form, make to greatest extent butane and alkene mixture change propylene into, the split product of ethene and other by products, and these split products are through after simple refrigerated separation, the separation system that is admitted to steam cracking device is carried out separating-purifying, take full advantage of the operation surplus of existing separation system, to improve propylene in existing steam cracking process, a kind of practicable method of ethylene yield.
The C 4 olefin that produces in the steam cracking process and paraffins mixture are the cracking c_4 treatment system of raw material, formed 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, fluidized-bed.
The catalyzer that uses in C _ 4 alkene catalytic pyrolysis reactor, butane catalytic cracking reaction device and mixed olefins and 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 aluminium, during modification, metal-salt used is carbonate, vitriol, nitrate, oxalate, phosphoric acid salt or the muriate of above-mentioned selected metal, can be also 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 feeding air speed scope is 0.5～100h -1
Mixed olefins and alkane catalytic cracking catalyst can with the carbon five that produces from carbon four cracking unit or more the olefin fraction of high carbon atom number be converted at least in part the catalytically cracked gas that is rich in propylene and ethene.The temperature of reaction of mixed olefins and alkane catalytic pyrolysis unit is 450～650 ℃, and reaction pressure is 0.07～0.50MPa, and during liquid, volume space velocity is 0.5～100h -1, the charging mass ratio of water vapour and butane and alkene mixture is 0～10.
The butane catalytic cracking catalyst can be converted into the catalytically cracked gas that is rich in propylene and ethene in whole or in part with 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
Cracking c_4 treatment system of the present invention raw material used 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, first by selective hydrogenation device removed wherein alkynes and Butadiene Extraction after remaining a small amount of divinyl.
In the present invention, mentioned catalyzer all can adopt existing catalyst preparation technology preparation, and the Beijing Chemical Research Institute can produce described catalyzer.
In sum, add the C 4 olefin that produces in the steam cracking device and paraffins mixture and be the cracking c_4 treatment system of raw material in steam cracking process, the product that this system is obtained carries out initial gross separation, and the product after separating passes into respectively the corresponding position of separation (recovery) system in 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 standby pyrolyzer.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.
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 ton/years 228.00 90.00 19.35 2.66
1,000,000 tons of olefin plant primary product yields of table 2 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) in C 4 olefin paraffins mixture (not containing diolefin), butene content is 95.9%, 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 take steam cracking device and through the butane after Butadiene Extraction and selective hydrogenation and alkene mixture as raw material, 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 the C 4 olefin in comparative example 1 and paraffins mixture raw material are sent into the C _ 4 alkene catalytic pyrolysis unit, catalytic cracking reaction occurs in the C 4 olefin in 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 catalyzer 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%, produced 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 the following cut of carbon five, and logistics 3 is for containing the above cut of carbon six of a small amount of carbon five.
(3) logistics 2 is passed in rectifying tower 1 in this catalytic pyrolysis system and separate, obtain logistics 4 and logistics 5, logistics 4 is the following component of carbon three, and logistics 5 is the above cut of carbon four.
(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 by C 4 olefin the alkene (being mainly that carbon five is to carbon eight) form;
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 passed into mixed olefins and alkane catalytic pyrolysis unit, temperature of reaction is 600 ℃, and reaction pressure is 0.15MPa, and during liquid, volume space velocity is 5h -1, the charging mass ratio of water vapour and butane and alkene mixture is 1.In this reaction member, the above alkene of most carbon four 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 of mixed olefins and the unit employing of alkane catalytic pyrolysis is the ZSM-5 molecular sieve type catalyzer 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 the following cut of carbon five, and logistics 9 is for containing the above cut of carbon six of a small amount of carbon five.
(6) logistics 8 is passed in rectifying tower 2 separate, obtain logistics 10 and logistics 11, logistics 10 is the following cut of carbon three, and logistics 11 is carbon four carbon five mixed fraction, logistics 11 and logistics 9 is mixed to get the logistics 12 of carbon four above cuts.
(7) cut 12 is passed into 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 catalyzer 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 the following cut of carbon five, and logistics 15 is the above cut of carbon six of a small amount of carbon five.
(9) logistics 14 is passed in rectifying tower 3 separate, obtain logistics 16 and logistics 17, logistics 16 is the following cut of carbon three, and logistics 17 is for containing carbon four mixed fraction of a 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 pass into 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, 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 32.18%, and the propylene total recovery is 18.19%.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 1.21%, propylene total recovery increase 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 take steam cracking device and through the butane after Butadiene Extraction and selective hydrogenation and alkene mixture as raw material, 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 comparative example 1 and paraffins mixture raw material after shortening is removed wherein a small amount of divinyl, send into the C _ 4 alkene catalytic pyrolysis unit, catalytic cracking reaction occurs in the C 4 olefin in 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 catalyzer 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%, produced 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 the following cut of carbon five, and logistics 3 is for containing the above cut of carbon six of a small amount of carbon five.
(3) logistics 2 is passed in rectifying tower 1 in this catalytic pyrolysis system and separate, obtain logistics 4 and logistics 5, logistics 4 is the following component of carbon three, and logistics 5 is the above cut of carbon four.
(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 by C 4 olefin the alkene (being mainly that carbon five is to carbon eight) form;
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 passed into mixed olefins and alkane catalytic pyrolysis unit, temperature of reaction is 600 ℃, and reaction pressure is 0.15MPa, and during liquid, volume space velocity is 5h -1, the charging mass ratio of water vapour and butane and alkene mixture is 1.In this reaction member, the above alkene of most carbon four 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 of mixed olefins and the unit employing of alkane catalytic pyrolysis is the ZSM-5 molecular sieve type catalyzer 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 the following cut of carbon five, and logistics 9 is for containing the above cut of carbon six of a small amount of carbon five.
(6) logistics 8 is passed in rectifying tower 2 separate, obtain logistics 10 and logistics 11, logistics 10 is the following cut of carbon three, and logistics 11 is for containing carbon four mixed fraction of 20wt% carbon five.
(7) cut 11 is passed into 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 catalyzer 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 the following cut of carbon five, and logistics 14 is for containing the above cut of carbon six of a small amount of carbon five.
(9) logistics 13 is passed in rectifying tower 3 separate, obtain logistics 15 and logistics 16, logistics 15 is the following cut of carbon three, and logistics 16 is for containing carbon four mixed fraction of a 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 pass into 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, 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 31.70%, and the propylene total recovery is 17.90%.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 0.73%, propylene total recovery increase by 2.23%.
This shows, in original steam cracking process process, the C 4 olefin that increase produces in the steam heat cracking technology and paraffins mixture are the cracking c_4 treatment system of raw material, in the situation that increase a small amount of catalytic cracking reaction device, the split product that takes full advantage 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 is conducive to 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: with cracking c_4 raffinate introducing C _ 4 alkene catalytic pyrolysis unit, described raw material is converted at least in part the catalytically cracked gas that is rich in propylene and ethene, is separated into the following cut of carbon three and the above cut of carbon four;
(2) mixed olefins and alkane catalytic pyrolysis: make the above cut of carbon four that step (1) obtains be converted at least in part the catalytically cracked gas that is rich in propylene and ethene in mixed olefins and alkane catalytic pyrolysis unit, be separated into the following cut of carbon three and the above cut of carbon four;
(3) butane catalytic pyrolysis: the above cut of carbon four that step (2) is obtained is sent into butane catalytic pyrolysis unit, make it be converted at least in part the catalytically cracked gas that is rich in propylene and ethene, be separated into the following cut of carbon three and the above cut of carbon four;
(4) product reclaims: the following cut of carbon three that step (1), step (2) and step (3) are obtained is 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 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, cooling and the separation with logistics 1, 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 at least in part the catalytically cracked gas logistics 4 that is rich in propylene and ethene, logistics 4 is cooling 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, cooling and the separation with logistics 7, 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 together 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 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, cooling and the separation with logistics 1, 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 at least in part the catalytically cracked gas logistics 4 that is rich in propylene and ethene, the cooling rear logistics of carbon six above cuts and the logistics of carbon five following cuts of first being separated into of logistics 4, then the logistics of carbon five following cuts is isolated the logistics 5 and the logistics 6 that contains the C-4-fraction of a small amount of carbon five of carbon three following cuts, logistics 6 is passed into 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, cooling and the separation with logistics 7, 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 together with logistics 2, with the propylene of raising steam cracking device and the output of ethene.
4. utilize as claimed in claim 2 or claim 3 the method for 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. utilize as claimed in claim 2 or claim 3 the method for cracking c_4 raffinate propylene enhancing and ethene, it is characterized in that, with the above cut recycle of the carbon five in the logistics 9 of described carbon four above cuts or send into the pyrolysis gasoline hydrogenation device.
6. utilize as claimed in claim 2 or claim 3 the method for cracking c_4 raffinate propylene enhancing and ethene, it is characterized in that, it is 0～100 ℃ that catalytically cracked gas carries out cooling temperature range with separating.
7. utilize as claimed in claim 2 or claim 3 the method for cracking c_4 raffinate propylene enhancing and ethene, it is characterized in that, it is 0～40 ℃ that catalytically cracked gas carries out cooling temperature range with separating.
8. utilize as claimed in claim 2 or claim 3 the method for cracking c_4 raffinate propylene enhancing and ethene, it is characterized in that, described C _ 4 alkene catalytic pyrolysis unit, the catalyzer of butane catalytic pyrolysis unit and mixed olefins and the unit use of alkane catalytic pyrolysis 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, one or more in tungsten or aluminium, during modification, metal-salt used is the carbonate of above-mentioned selected metal, vitriol, nitrate, oxalate, phosphoric acid salt, muriate or corresponding ammonium salt.
9. utilize as claimed in claim 2 or claim 3 the method for 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 during liquid, volume space velocity is 0.5～100h -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 during liquid, volume space velocity is 0.5～100h -1, the charging mass ratio of water vapour and butane and alkene mixture is 0～10; The temperature of reaction of described butane catalytic pyrolysis unit 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 first removed by alkynes and divinyl that selective hydrogenation is incited somebody to action wherein, then sends into described cracking c_4 cut treatment system.
CN2010102044006A 2010-06-18 2010-06-18 Method for increase production of propylene and ethylene by pyrolyzing C4 raffinate Active CN102286292B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2010102044006A CN102286292B (en) 2010-06-18 2010-06-18 Method for increase production of propylene and ethylene by pyrolyzing C4 raffinate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2010102044006A CN102286292B (en) 2010-06-18 2010-06-18 Method for increase production of propylene and ethylene by pyrolyzing C4 raffinate

Publications (2)

Publication Number Publication Date
CN102286292A CN102286292A (en) 2011-12-21
CN102286292B true CN102286292B (en) 2013-11-06

Family

ID=45333056

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2010102044006A Active CN102286292B (en) 2010-06-18 2010-06-18 Method for increase production of propylene and ethylene by pyrolyzing C4 raffinate

Country Status (1)

Country Link
CN (1) CN102286292B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN114478175B (en) * 2020-11-13 2024-08-16 中国石化工程建设有限公司 System and method for increasing yield of low-carbon olefin
CN114931970B (en) * 2022-04-18 2023-10-13 中国石油大学(华东) Catalyst for preparing ethylene and propylene by catalytic pyrolysis of low-carbon olefin and method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101092325A (en) * 2006-06-21 2007-12-26 中国石油化工股份有限公司 Method for preparing propylene by catalytic cracking olefin of containing carbon
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101092325A (en) * 2006-06-21 2007-12-26 中国石油化工股份有限公司 Method for preparing propylene by catalytic cracking olefin of containing carbon
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

Also Published As

Publication number Publication date
CN102286292A (en) 2011-12-21

Similar Documents

Publication Publication Date Title
CN102285852B (en) Utilize the method for refinery C four increasing output of ethylene and propylene
CN101844960B (en) Method for producting propylene by catalytic pyrolysis of liquefied gas
CN101255086B (en) Method for cracking C_4 and preparing olefin by refinery C_4
CN101172923A (en) Combination technique for producing olefin hydrocarbon with mixed C_4
CN102285851B (en) Method for increasing yields of ethylene and propylene
CN102286296B (en) Method for increase production of propylene and ethylene
CN101585747B (en) Method for transforming oxygenates into propylene
CN102286292B (en) Method for increase production of propylene and ethylene by pyrolyzing C4 raffinate
CN103864564B (en) Technique for processing methanol-to-propylene by-products
CN102286297B (en) Method for increase production of propylene and ethylene
CN102070390B (en) The method of refinery's mixed c 4 propylene
CN104557368A (en) System for preparing ethylene, ethylene and arene from kinds of raw materials by coupling and transformation and method for system
CN103864563B (en) Method for preparing aromatic hydrocarbon from hydrocarbon tail oil byproducts produced in coal-based methanol to propylene process
CN103834437B (en) Technological process for aromatization of low-carbon hydrocarbon
CN103121891A (en) Method for producing low-carbon olefin
CN105295993B (en) A kind of method of modified version liquefied gas through aromatization
CN102285857B (en) Method for increasing yields of propylene and ethylene
CN102285853A (en) Method for increasing yield of propylene and ethylene by using cracked C4 as raw material
CN102285854B (en) Method for increasing yields of propylene, ethylene and butadiene
CN102899084B (en) Method for co-production of ethylene cracking raw material by aromatization of carbon tetrad
CN110041157B (en) Method for improving yield of propylene prepared from methanol and prolonging service life of catalyst
CN102285856A (en) Method for increasing yields of propylene and ethylene
CN103834435B (en) Two-stage reaction process for hydro-aromatization of carbon-four liquefied gas
CN101870632A (en) Method for producing low-carbon olefin
CN101857520B (en) Method for increasing yield of propylene and ethylene

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant