CN102285853A - Method for increasing yield of propylene and ethylene by using cracked C4 as raw material - Google Patents
Method for increasing yield of propylene and ethylene by using cracked C4 as raw material Download PDFInfo
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Abstract
The invention relates to a method for increasing the yield of propylene and ethylene in a steam-cracking process. The steam-cracking process comprises a cracking furnace and a separating (recovering) system, a cracked-C4 processing system using a C4-alkane and alkene mixture produced in the steam-cracking process as a raw material is added on the basis, the C4-alkane and alkene mixture is converted into a cracking product which is rich in the propylene and the ethylene through catalytic-cracking reaction and oxidative-cracking reaction, and the cracking product is then sent back to the separating (recovering) system of a catalytic-cracking device to finish the separation and the purification of the cracking product. The method has the characteristics that catalytic-cracking and oxidative-cracking reactors and simple separating equipment are only added, the potential of the separating (recovering) system of a traditional steam-cracking device is fully exploited, the yield of the propylene and the ethylene is increased, and meanwhile, C4 alkane and alkene generated by the steam-cracking device can be fully converted by combining the advantages of catalytic cracking and oxidative cracking. The method can be used for the traditional steam-cracking device, the utilization efficiency of the raw material is improved, and the economic income of enterprises is increased.
Description
Technical field
The present invention relates to the method for a kind of propylene enhancing and ethene.Especially, the present invention relates to a kind of butane and alkene mixture that utilizes preparing ethylene by steam cracking technology to produce and be raw material, improve the ethene of steam cracking process system ethylene unit and the method for propone output.
Background technology
Ethene and propylene are important basic chemical raw materials.In Industrial processes, ethene and propylene are mainly by steam cracking (being thermo-cracking) explained hereafter.In the steam cracking production equipment, cracking stocks such as lighter hydrocarbons, petroleum naphtha, hydrogenation tail oil, solar oil are with after water vapour mixes, heat scission reaction takes place in pyrolyzer, generates split products such as hydrogen, methane, carbon two, carbon three, carbon four, carbon five, pyrolysis gasoline, Pyrolysis fuel oil PFO and coke.Split product fractionation in follow-up separation (recovery) system is purified, and obtains the cut of different carbonatomss, isolates ethene and propylene product again from carbon two, C3 fraction.
Along with China's rapid growth of economy, downstream industry increases fast to the demand of ethene and propylene.Add derived product net importation amount according to the apparent consumption of ethene and amount to the equivalent consumption of calculating estimation, China's ethene degree of self-sufficiency in 2008 only has 54%.In order to satisfy the ever-increasing demand of downstream industry, alleviate imbalance between supply and demand, the ethene production capacity of China also enlarges rapidly.In recent years, some ethylene projects newly-built or enlarging are gone into operation successively, and other has a collection of ethylene project in process of construction.Newly-increased ethene production capacity need increase considerably the supply of cracking stock, yet domestic oil-refining capacity is difficult to quick growth, cause that cracking stock is in short supply, quality descends, and makes the actual load of separation (recovery) system in the steam cracking process be lower than its designed productive capacity.So the throughput of improve the cracking stock utilising efficiency, giving full play to cracker will become the important factor that influences the business economic benefit.
The split product that generates in the steam cracking device obtains the cut of different carbonatomss after separating, wherein the main component of cracking c_4 cut is divinyl, butylene, butane and a small amount of butine.After product butadiene was isolated in extracting through divinyl, remaining cracking c_4 was the mixture of C 4 olefin and alkane, and wherein the content of butylene is more than the 70wt%.This part C 4 olefin and paraffins mixture account for 4～10wt% of steam cracking product total amount, but generally are used for civil LPG, and added value of product is lower.Along with civil LPG is replaced by more cheap Sweet natural gas gradually, people wish for cracking c_4 alkene and alkane seek added value higher utilize approach, and it is cracked into ethene and a kind of just potential processing scheme of propylene.At present, it is the research of low-carbon alkenes such as ethene, propylene that existing in the world many companies have carried out C 4 olefin and alkane cracking, and has obtained bigger progress, and technology such as catalytic pyrolysis, oxicracking and catalytic dehydrogenation and associated catalysts all have report.These schemes are expected to improve the utilising efficiency of cracking stock, obtain the low-carbon alkene product of more high added value.Simultaneously, the split product of C 4 olefin and alkane can also utilize (recovery) system separation purification that separates of steam cracking device to obtain ethene and propylene product, excavates existing production potential of separating (recovery) system.
Catalytic pyrolysis process can be converted into C 4 olefin propylene and ethene effectively, and temperature of reaction can be far below existing steam cracking process, and the catalytic pyrolysis product is formed similar to the steam cracking product.The speed of reaction of alkane in catalytic cracking reaction is far below alkene, and especially at a lower temperature, the butane reaction is slower.And in the oxicracking process, owing to introduced oxygen, broken the thermodynamics equilibrium limit of hydrocarbon cracking, and can accelerate the dehydrogenation reaction of alkane, promote the carbon bond fracture, reduce the apparent activation energy of reaction.Therefore, the oxicracking process not only can make raw material near transforming fully, can also make also fully cracking of alkane.In addition, the oxicracking process is thermopositive reaction, does not need additionally to provide fuel to keep temperature of reaction.
Summary of the invention
The present invention is in order to improve the utilising efficiency of cracking stock in the steam cracking process, make full use of cracking c_4 alkane and alkene, having proposed increases the cracking c_4 treatment system in existing steam cracking process, utilize butane that steam cracking process produces and the alkene mixture method for raw material producing more propylene and ethene.
Method provided by the invention is a raw material with butane and the alkene mixture that steam cracking process produces, combine catalytic pyrolysis process and oxicracking process, utilize catalytic cracking reaction to make that most of C 4 olefin is cracked into propylene in butane and the alkene mixture in the catalytic pyrolysis system, ethene and other byproducts, utilize the oxicracking process to make again to fail in the catalytic pyrolysis process materials such as butane that fully transform further to react generation ethene, propylene and other oxicracking products, alkene and alkane in the described catalytically cracked gas can both fully be transformed, effectively improved the output of propylene and ethene.The present invention catalytic pyrolysis system and oxicracking system are produced and simple separation after logistics send into steam cracking device again separate (recoverys) system, can fully excavate the production potential of existing separation (recovery) system.So just can improve the propylene and the ethylene yield of steam cracking device by increasing the cracking c_4 treatment system that is raw material with the butane that produces in the steam cracking process and alkene mixture.
Concrete technical scheme is as follows:
The method of propylene enhancing of the present invention and ethene, in steam cracking and tripping device, set up the cracking c_4 cut treatment system that comprises catalytic pyrolysis unit and oxicracking unit, described method is a raw material with butane and the alkene mixture that steam cracking process produces, and may further comprise the steps:
(1) carbon four catalytic pyrolysiss: butane and alkene mixture are drawn from steam cracking and tripping device, send into the catalytic pyrolysis unit, described butane and alkene mixture are converted into the catalytically cracked gas that is rich in propylene and ethene at least in part;
(2) oxicracking: from the catalytically cracked gas that step (1) obtains, isolate the logistics that contains butane, it is sent into the oxicracking unit, make the described logistics that contains butane be converted into the oxicracking gas that is rich in ethene and propylene at least in part;
(3) product reclaims: isolate carbon three following cuts in the oxicracking gas that obtains catalytically cracked gas that obtains from step (1) and the step (2), it is sent in the splitting gas of oil scrubber, water wash column or compressor of steam cracking and tripping device, to improve the propylene and the ethylene yield of steam cracking device.
Preferably, in described catalytic pyrolysis unit, described butane and alkene mixture are converted into the catalytically cracked gas logistics 1 that is rich in propylene and ethene at least in part, be separated into the logistics 2 of carbon three following cuts and the logistics 3 of carbon four above cuts after the cooling, described carbon four above cuts 3 are sent into described oxicracking unit, in described oxicracking unit, described carbon four above cuts 3 are converted into the oxicracking gas logistics 4 that is rich in ethene and propylene at least in part, the logistics 5 that obtains carbon three following cuts is separated in logistics 4 cooling backs, logistics 5 is sent into the oil scrubber of steam cracking and tripping device with logistics 2, in the splitting gas of water wash column or compressor, to improve the propylene and the ethylene yield of steam cracking device.
More preferably, also be provided with higher carbon number hydrocarbon catalytic pyrolysis unit in the cracking c_4 treatment system of this method, this method may further comprise the steps:
(1) carbon four catalytic pyrolysiss: butane and alkene mixture are drawn from steam cracking and tripping device, send into carbon four catalytic pyrolysis unit, described butane and alkene mixture are converted into the catalytically cracked gas that is rich in propylene and ethene at least in part;
(2) higher carbon number hydrocarbon catalytic pyrolysis: from the catalytically cracked gas that step (1) obtains, isolate the logistics that contains carbon four above hydro carbons, it is sent into higher carbon number hydrocarbon catalytic pyrolysis unit, the described logistics that contains carbon four above hydro carbons is converted into the catalytically cracked gas that is rich in propylene and ethene at least in part;
(3) oxicracking: from the catalytically cracked gas that step (2) obtains, isolate the logistics that contains butane, it is sent into the oxicracking unit, make the described logistics that contains butane be converted into the oxicracking gas that is rich in ethene and propylene at least in part;
(4) product reclaims: isolate carbon three following cuts in the oxicracking gas that obtains catalytically cracked gas that obtains from step (1) and step (2) and the step (3), it is sent in the splitting gas of oil scrubber, water wash column or compressor of steam cracking and tripping device, to improve the propylene and the ethylene yield of steam cracking device.
Preferably, in described carbon four catalytic pyrolysis unit, described butane and olefin mixture feed are converted into the catalytically cracked gas logistics 1 that is rich in propylene and ethene at least in part, be separated into the logistics 2 of carbon three following cuts and the logistics 3 of carbon four above cuts after the cooling, described higher carbon number hydrocarbon catalytic pyrolysis unit is sent in logistics 3, make the logistics 3 of described carbon four above cuts be converted into the catalytically cracked gas logistics 6 that is rich in propylene and ethene at least in part, catalytically cracked gas logistics 6 is separated into the logistics 7 of carbon three following cuts and the logistics 8 of carbon four above cuts, the oxicracking system is sent in logistics 8, make the logistics 8 of described carbon four above cuts be converted into the oxicracking gas logistics 4 that is rich in ethene and propylene at least in part, the logistics 5 of carbon three following cuts will be isolated after logistics 4 coolings, with logistics 5, logistics 2 is sent into the oil scrubber that steam cracking device separates (recovery) system with logistics 7, in the splitting gas of water wash column or compressor, to improve the propylene and the ethylene yield of steam cracking device.
Preferably, described catalytically cracked gas logistics 1 cooling back gas-liquid separation, obtain the logistics of carbon five following cuts and the logistics of carbon six above cuts, logistics with carbon five following cuts is separated into the logistics 2 of carbon three following cuts and the logistics of carbon four carbon five mixed fraction then, again with the logistics of carbon six above cuts and the logistics 3 that obtains carbon four above cuts after the logistics of carbon four carbon five mixed fraction mixes; Described oxicracking gas logistics 4 cooling back gas-liquid separations obtain the logistics of carbon six above cuts and the logistics of carbon five following cuts, isolate the logistics 5 of carbon three following cuts then from the logistics of carbon five following cuts; The described catalytically cracked gas logistics 6 cooling first gas-liquid separations in back obtain the logistics of carbon six above cuts and the logistics of carbon five following cuts, from the logistics of carbon five following cuts, isolate the logistics 7 of carbon three following cuts then, again with the logistics of carbon six above cuts and the logistics 8 that obtains carbon four above cuts after the logistics of carbon four carbon five mixed fraction mixes.
Preferably, butane and the alkene mixture that described steam cracking process is produced sent into hydrogenation unit earlier, make the divinyl and the butine of the overwhelming majority in butane and the alkene mixture be converted into butylene, more described butane and alkene mixture are sent into described cracking c_4 treatment system.
Preferably, the catalyzer that described oxicracking unit uses is conventional oxicracking catalyzer, for supporting the catalyzer of precious metal on the different carriers with regular or non-regular pore passage structure.
Preferably, described method also is provided with carbon monoxide and removes the unit, before sending into steam cracking and tripping device, described cracking c_4 treatment system generation and isolated carbon three following cuts are admitted to carbon monoxide and remove the unit, to remove wherein most carbon monoxide or carbon monoxide is converted into carbonic acid gas.
Preferably, described method also is provided with the acid gas removal unit, before sending into steam cracking and tripping device, described cracking c_4 treatment system produces and isolated carbon three following cuts are admitted to the acid gas removal unit, to remove wherein carbonic acid gas and other sour gas of the overwhelming majority.
Preferably, described method also is provided with oxygen and removes the unit, and before sending into steam cracking and tripping device, described cracking c_4 treatment system produces and isolated carbon three following cuts are admitted to oxygen and remove the unit and remove wherein most oxygen.
Preferably, isolate the logistics of carbon five above cuts catalytically cracked gas that produces from described cracking c_4 treatment system and the oxicracking gas, with its recycle or deliver to the pyrolysis gasoline hydrogenation device.
Preferably, described catalytically cracked gas and oxicracking gas cool off with isolating temperature range be 0～100 ℃, preferred 0～40 ℃.
Preferably, the catalyzer of described carbon four catalytic pyrolysis unit and higher carbon number hydrocarbon catalytic pyrolysis unit use is one or more of modification or unmodified SAPO-34, ZSM-5, ZSM-11, ZSM-23, MCM-22, MCM-49, MCM-56 and 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, and used metal-salt is carbonate, vitriol, nitrate, oxalate, phosphoric acid salt, muriate or the corresponding ammonium salt of above-mentioned selected metal during modification.
Preferably, the unitary 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, the charging mass ratio of water vapour and butane and alkene mixture is 0～10; The unitary temperature of reaction of described oxicracking is 500～900 ℃, and reaction pressure is 0.07～0.50MPa, and volume space velocity is 0.5～100h during liquid
-1, the charging mass ratio of oxygen and hydrocarbon raw material is 0.05～2; The unitary temperature of reaction of described higher carbon number hydrocarbon catalytic pyrolysis is 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.
For the oxicracking unit, in described oxicracking unit, use catalyzer, to regulate each product selectivity in the oxidative cracking reaction.The catalyzer that described oxicracking unit uses is conventional oxicracking catalyzer, and its compositing characteristic is to support precious metals such as platinum, palladium on the different carriers (as the molecular sieve of aluminum oxide, silicon oxide, kaolin, clay and different pore passage structures) with regular or non-regular pore passage structure.
The present invention is outside existing steam cracking and tripping device system, only need to increase with the butane of steam cracking and tripping device generation and the cracking c_4 treatment system that alkene mixture is raw material, utilize catalytic cracking reaction process and oxidative cracking reaction process to combine, make butane and alkene mixture change the split product of propylene, ethene and other by-products into, and after the simple refrigerated separation of these split products processes, separation (recovery) system that is admitted to steam cracking process separates purification.
The cracking c_4 treatment system comprises carbon four catalytic pyrolysis unit, oxicracking unit and separating unit.The unitary raw material of carbon four catalytic pyrolysiss is butane and the alkene mixture that steam cracking and tripping device produce, and this raw material is converted into the catalytically cracked gas that is rich in propylene and ethene in carbon four catalytic pyrolysis unit.Carbon four catalytic pyrolysis unit can adopt one or more combination in fixed-bed reactor, moving-burden bed reactor, the fluidized-bed reactor.The catalytically cracked gas that carbon four catalytic pyrolysis unit produce is cooled and separates and obtains carbon three following cuts and carbon four above cuts, above-mentioned carbon three following cuts are sent into the appropriate location that steam cracking device separates (recovery) system, and carbon four above cuts are completely or partially sent into the oxicracking system.
Carbon four catalytic pyrolysis unit can adopt one or more of modification or unmodified SAPO-34, ZSM-5, ZSM-11, ZSM-23, MCM-22, MCM-49, MCM-56 and 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.Carbon four catalytic cracking catalysts 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 butane and the alkene mixture.The unitary temperature of reaction of 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, the charging mass ratio of water vapour and butane and alkene mixture is 0～10.
The unitary raw material of oxicracking can be by separating the whole carbon four above cuts that obtain in the catalytically cracked gas of carbon four catalytic pyrolysis unit generation, it also can be the part of these carbon four above cuts, especially, also can be carbon four carbon five parts in these carbon four above cuts.Above-mentioned raw materials is converted into the oxicracking gas that is rich in ethene, propylene in the oxicracking unit.The oxicracking unit can use catalyzer, also can not use catalyzer.The oxicracking unit can adopt oxygen or air as oxygenant.The oxicracking unit adopts one or more combination in tubular reactor, fixed-bed reactor, moving-burden bed reactor, the fluidized-bed reactor.The catalytically cracked gas that the oxicracking unit produces is cooled and separates and obtains carbon three following cuts and carbon four above cuts, and above-mentioned carbon three following cuts are sent into the appropriate location that steam cracking device separates (recovery) system.
The unitary temperature of reaction of oxicracking is 500～900 ℃, and reaction pressure is 0.07～0.50MPa, and oxygen or airborne oxygen and oxicracking material feeding mass ratio are 0.05～2.If the oxicracking unit uses catalyzer, then volume space velocity is 0.5～100h during liquid
-1The catalyzer that the oxicracking unit uses can be conventional oxicracking catalyzer, and its compositing characteristic is to support precious metals such as platinum, palladium on the different carriers (as the molecular sieve of aluminum oxide, silicon oxide, kaolin, clay and different pore passage structures) with regular or non-regular pore passage structure.
The cracking c_4 treatment system can also comprise higher carbon number hydrocarbon catalytic pyrolysis unit.The unitary raw material of this higher carbon number hydrocarbon catalytic pyrolysis be in the catalytically cracked gas that from carbon four cracking unit, produces carbon four or more high carbon atom count cut, this raw material is converted into the catalytically cracked gas that is rich in propylene, ethene in higher carbon number hydrocarbon catalytic pyrolysis unit.Higher carbon number hydrocarbon catalytic pyrolysis unit can adopt one or more combination in fixed-bed reactor, moving-burden bed reactor, the fluidized-bed reactor.The catalytically cracked gas that higher carbon number hydrocarbon catalytic pyrolysis unit produces is cooled and separates and obtains carbon three following cuts and carbon four above cuts, above-mentioned carbon three following cuts are sent in the splitting gas of oil scrubber, water wash column or compressor that steam cracking device separates (recoverys) system, with the propylene and the ethylene yield of raising steam cracking device.
The higher carbon number hydrocarbon catalytic cracking catalyst can adopt one or more of modification or unmodified SAPO-34, ZSM-5, ZSM-11, ZSM-23, MCM-22, MCM-49, MCM-56 and 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 higher carbon number hydrocarbon catalytic cracking catalyst can with the carbon five that from carbon four cracking unit, produces or more high carbon atom count cut and be converted into the catalytically cracked gas that is rich in propylene, ethene at least in part.The unitary temperature of reaction of higher carbon number hydrocarbon catalytic pyrolysis is 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.
Mentioned catalyzer all can adopt existing catalyst preparation technology preparation among the present invention, and the Beijing Chemical Research Institute can produce described catalyzer.
The raw material that the present invention adopts is butane and the alkene mixture that steam cracking process produces, and this raw material can be through butane and alkene mixture after the divinyl extracting, and this raw material can be removed wherein divinyl and butine through a hydrogenation unit.
Method provided by the invention can comprise that a carbon monoxide removes the unit, is used for removing the carbon monoxide in the logistics of the carbon three following cuts that the cracking c_4 treatment system produces.
Method provided by the invention can comprise a CO2 removal unit, is used for removing the carbonic acid gas in the logistics of the carbon three following cuts that the cracking c_4 treatment system produces.
Method provided by the invention can comprise that an oxygen removes the unit, is used for the oxygen in the logistics of the carbon three following cuts that the cracking c_4 treatment system produces.
In sum, in existing steam cracking process, add the cracking c_4 treatment system that the butane that produces with steam cracking process and alkene mixture are raw material, make butane and olefin mixture feed partly be converted into propylene and ethene, catalytic pyrolysis product and oxicracking product that this cracking c_4 treatment system is produced carry out initial gross separation, and each logistics that separation obtains is sent into the appropriate location of separation (recovery) system in the steam cracking process, thereby improved the output of the utilising efficiency of raw material and propylene, ethene, 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, 1 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 | Hydrogenation tail oil | 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, and mixed pyrolysis gas is through after separating (recoverys) system and separating purification, and 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, produce with steam cracking process and be raw material through butane and alkene mixture after the divinyl extracting, the propylene and the ethene of volume increase steam cracking device.The cracking c_4 treatment system comprises carbon four catalytic pyrolysis unit, oxicracking 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 carried out the catalytic dehydrogenation processing, make wherein most divinyl and butine be converted into butylene, then it is sent into carbon four 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 550 ℃, reaction pressure (gauge pressure) are 3h for 0.15MPa, air speed
-170% C 4 olefin generation catalytic cracking reaction generates low-carbon alkene and carbon five above 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 carbon four catalytic pyrolysis unit adopt is the ZSM-5 molecular sieve type catalyst of modification, it consists of: (silica alumina ratio is 100 for phosphorus 5wt%, lanthanum 2wt%, ZSM-5 molecular sieve 64wt%, particle diameter is 500nm), silicon oxide 29wt%, produce by the Beijing Chemical Research Institute.
(2) with logistics 1 cooling and rectifying separation, obtain 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) logistics 2 is compressed to rectifying separation behind the suitable pressure, obtains logistics 4 and logistics 5, logistics 4 is carbon three following cuts, and logistics 5 is carbon four carbon five mixed fraction.
(4) logistics 3 is mixed with logistics 5, obtain logistics 6, logistics 6 is composed as follows:
1) butane, its content are 7.56wt%
2) C 4 olefin, its content are 52.47wt%;
3) carbon five is to carbon eight alkane, and its content is 11.80wt%;
4) carbon five is to carbon eight alkene, and its content is 25.25wt%
5) aromatic hydrocarbons, its content are 1.00wt%.
(5) logistics 6 is fed the oxicracking unit, simultaneously to oxicracking unit aerating oxygen, the mass ratio of oxygen and logistics 6 is 0.5.The oxicracking unit is catalyst filling not, and its temperature of reaction is that 700 ℃, reaction pressure (gauge pressure) are 6h for 0.20MPa, air speed
-1Oxidative cracking reaction takes place in the oxygen of the most logistics 6 and the overwhelming majority in the oxicracking unit, generate the logistics 7 that is rich in ethene, propylene, and therein ethylene content is 28.1wt%, and propylene content is 14.7wt%.
(6) with logistics 7 coolings, separate obtaining logistics 8 and 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.
(7) logistics 8 is compressed to rectifying separation behind the suitable pressure, obtains logistics 10 and logistics 11, logistics 10 carbon three following cuts wherein, logistics 11 is carbon four carbon pentaene hydrocarbon and aliphatic fractions.
(8) with logistics 11 rectifying separation in oxicracking system separating unit, obtain logistics 12 and logistics 13, wherein logistics 12 is a C-4-fraction, and logistics 13 is C5 fraction.
(9) logistics 13 is mixed with logistics 9, form logistics 14, logistics 14 is carbon five above cuts.
(10) logistics 14 is sent into the pyrolysis gasoline hydrogenation device of steam cracking process.
(11) logistics 12 is sent into the liquefied petroleum gas (LPG) production plant of steam cracking process.
(12) logistics 10 and logistics 4 are mixed into logistics 15, carbon monoxide are sent in logistics 15 removed the unit, change carbon monoxide most in the logistics 15 into carbonic acid gas, obtain logistics 16.
(13) the CO2 removal unit is sent in logistics 16, the most CO2 removal with in the logistics 16 obtain logistics 17.
(14) temperature of control logistics 17 is in 230～250 ℃ of scopes, and controls its pressure greater than 0.7MPa, in the splitting gas pipeline in the oil scrubber in separation (recovery) system of logistics 17 feeding steam cracking process.
Calculate and to get by the state of arts in the present embodiment, in existing steam cracking device, added be the catalytic pyrolysis-oxicracking system of raw material with C 4 olefin and paraffins mixture after, total system ethene total recovery reaches 32.29wt%, and the propylene total recovery reaches 17.65wt%.With respect to comparative example 1, the yield of ethene in the present embodiment has improved 1.32wt%, and propene yield has improved 1.98wt%.
Embodiment 2
Adopt the preferred method of the present invention, on the basis of comparative example 1, increase the cracking c_4 treatment system, produce with steam cracking process and be raw material through butane and alkene mixture after the divinyl extracting, the propylene and the ethene of volume increase steam cracking device.The cracking c_4 treatment system comprises carbon four catalytic pyrolysis unit, higher carbon number hydrocarbon catalytic pyrolysis unit, oxicracking 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 carbon four 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 550 ℃, reaction pressure (gauge pressure) are 3h-1 for 0.15MPa, air speed.70% C 4 olefin generation catalytic cracking reaction generates low-carbon alkene and carbon five above 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 carbon four catalytic pyrolysis unit adopt is the ZSM-5 molecular sieve type catalyst of modification, it consists of: (silica alumina ratio is 100 for phosphorus 5wt%, lanthanum 0.5wt%, ZSM-5 molecular sieve 64wt%, particle diameter is 500nm), silicon oxide 29wt%, produce by the Beijing Chemical Research Institute.
(2) with logistics 1 cooling, separate, obtain logistics 2 and logistics 3, wherein logistics 2 is carbon three following cuts, and logistics 3 is carbon cut more than four.Logistics 3 composed as follows:
1) butane, content are 7.56wt%;
2) C 4 olefin, content are 52.47wt%;
3) carbon five is to carbon eight alkane, and content is 11.80wt%;
4) carbon five is to carbon eight alkene, and content is 25.25wt%;
5) aromatic hydrocarbons, content are 1.00wt%.
(3) logistics 3 is sent into higher carbon number hydrocarbon catalytic pyrolysis unit, made logistics 3 under catalyst action catalytic cracking reaction take place, temperature of reaction is that 600 ℃, reaction pressure (gauge pressure) are 3h for 0.15MPa, air speed
-1Most of carbon four in the logistics 3 is to carbon eight alkene and alkane generation catalytic cracking reaction, the logistics 4 that logistics 3 is changed into be rich in propylene and ethene, and wherein the propylene content in the logistics 4 is 23.7wt%, ethylene content is 7.4wt%.This used catalyzer in higher carbon number hydrocarbon catalytic pyrolysis unit consists of: phosphorus 4wt%, lanthanum 3wt%, calcium 2wt%, silver-colored 2wt%, ZSM-5 molecular sieve 60wt% (silica alumina ratio is 140, and particle diameter is 400nm), silicon oxide 29wt%, produced by the Beijing Chemical Research Institute.
(4) with logistics 4 coolings, separate, obtain logistics 5 and logistics 6, wherein logistics 5 is carbon five following cuts, and logistics 6 is for containing the carbon six above cuts of small amount of carbon five following cuts.
(5) logistics 5 is compressed to rectifying separation behind the suitable pressure, obtains logistics 7 and logistics 8, logistics 7 is carbon three following cuts, and logistics 8 is carbon four carbon five mixed fraction.
(6) logistics 8 and logistics 6 are mixed the logistics 9 that obtains carbon four above cuts, the oxicracking unit is sent in logistics 9, simultaneously oxygen is sent into this oxicracking unit, the mass ratio of oxygen and logistics 10 is 0.8.Oxicracking unit catalyst filling is to improve the products distribution of oxidative cracking reaction.Temperature of reaction in the oxicracking unit is that 650 ℃, reaction pressure (gauge pressure) are 3h for 0.20MPa, air speed
-1Oxidative cracking reaction takes place in most logistics 10 and 99% oxygen in the oxicracking unit, generate the logistics 11 that is rich in ethene, propylene, and therein ethylene content is 28.3wt%, and propylene content is 14.9wt%.The catalyzer that this oxicracking unit adopts is the aluminum oxide of load platinum.
(7) with logistics 11 coolings, separate, obtain logistics 12 and logistics 13, wherein logistics 12 is carbon five following cuts, and logistics 13 is for containing the carbon six above cuts of small amount of carbon five following cuts.
(8) logistics 12 is compressed to rectifying separation behind the suitable pressure, obtains logistics 14 and logistics 15, logistics 14 is carbon three following cuts, and logistics 15 is carbon four carbon five mixed fraction.
(9) logistics 8 is mixed with logistics 15, obtain logistics 16, this logistics 16 is carbon four carbon five mixed fraction.
(10) with logistics 16 rectifying separation, obtain logistics 17 and logistics 18, wherein logistics 17 is C-4-fractions, logistics 18 is C5 fractions.
(11) logistics 18, logistics 6 and logistics 13 are mixed, obtain logistics 19, this logistics 19 is carbon five above cuts.
(12) logistics 19 is sent into the pyrolysis gasoline hydrogenation device of steam cracking process.
(13) logistics 17 is sent into the liquefied petroleum gas (LPG) production plant of steam cracking process.
(14) logistics 7 is mixed with logistics 14, obtain logistics 20, oxygen is sent in logistics 20 removed the unit, oxygen most in the logistics 20 is removed, obtain logistics 21.
(15) temperature of control logistics 21 is in 230～250 ℃ of scopes, and controls its pressure greater than 0.7MPa, in the splitting gas pipeline in the oil scrubber in separation (recovery) system of logistics 21 feeding steam cracking process.
Calculate and can get by the state of arts in the present embodiment, in existing steam cracking device, added be the cracking c_4 treatment system of raw material with C 4 olefin and paraffins mixture after, total system ethene total recovery reaches 32.25wt%, the propylene total recovery reaches 18.22wt%.With respect to comparative example 1, the yield of ethene in the present embodiment has improved 1.28wt%, and propene yield has improved 2.55wt%.
Claims (14)
1. the method for propylene enhancing and ethene, it is characterized in that, in steam cracking and tripping device, set up the cracking c_4 cut treatment system that comprises catalytic pyrolysis unit and oxicracking unit, described method is a raw material with butane and the alkene mixture that steam cracking process produces, and may further comprise the steps:
(1) carbon four catalytic pyrolysiss: butane and alkene mixture are drawn from steam cracking and tripping device, send into the catalytic pyrolysis unit, described butane and alkene mixture are converted into the catalytically cracked gas that is rich in propylene and ethene at least in part;
(2) oxicracking: from the catalytically cracked gas that step (1) obtains, isolate the logistics that contains butane, it is sent into the oxicracking unit, make the described logistics that contains butane be converted into the oxicracking gas that is rich in ethene and propylene at least in part;
(3) product reclaims: isolate carbon three following cuts in the oxicracking gas that obtains catalytically cracked gas that obtains from step (1) and the step (2), it is sent in the splitting gas of oil scrubber, water wash column or compressor of steam cracking and tripping device, to improve the propylene and the ethylene yield of steam cracking device.
2. the method for propylene enhancing as claimed in claim 1 and ethene, it is characterized in that, in described catalytic pyrolysis unit, described butane and alkene mixture are converted into the catalytically cracked gas logistics 1 that is rich in propylene and ethene at least in part, be separated into the logistics 2 of carbon three following cuts and the logistics 3 of carbon four above cuts after the cooling, described carbon four above cuts 3 are sent into described oxicracking unit, in described oxicracking unit, described carbon four above cuts 3 are converted into the oxicracking gas logistics 4 that is rich in ethene and propylene at least in part, the logistics 5 that obtains carbon three following cuts is separated in logistics 4 cooling backs, logistics 5 is sent into the oil scrubber of steam cracking and tripping device with logistics 2, in the splitting gas of water wash column or compressor, to improve the propylene and the ethylene yield of steam cracking device.
3. the method for propylene enhancing as claimed in claim 1 and ethene is characterized in that, also is provided with higher carbon number hydrocarbon catalytic pyrolysis unit in the cracking c_4 treatment system of this method, and this method may further comprise the steps:
(1) carbon four catalytic pyrolysiss: butane and alkene mixture are drawn from steam cracking and tripping device, send into carbon four catalytic pyrolysis unit, described butane and alkene mixture are converted into the catalytically cracked gas that is rich in propylene and ethene at least in part;
(2) higher carbon number hydrocarbon catalytic pyrolysis: from the catalytically cracked gas that step (1) obtains, isolate the logistics that contains carbon four above hydro carbons, it is sent into higher carbon number hydrocarbon catalytic pyrolysis unit, the described logistics that contains carbon four above hydro carbons is converted into the catalytically cracked gas that is rich in propylene and ethene at least in part;
(3) oxicracking: from the catalytically cracked gas that step (2) obtains, isolate the logistics that contains butane, it is sent into the oxicracking unit, make the described logistics that contains butane be converted into the oxicracking gas that is rich in ethene and propylene at least in part;
(4) product reclaims: isolate carbon three following cuts in the oxicracking gas that obtains catalytically cracked gas that obtains from step (1) and step (2) and the step (3), it is sent in the splitting gas of oil scrubber, water wash column or compressor of steam cracking and tripping device, to improve the propylene and the ethylene yield of steam cracking device.
4. the method for propylene enhancing as claimed in claim 3 and ethene, it is characterized in that, in described carbon four catalytic pyrolysis unit, described butane and olefin mixture feed are converted into the catalytically cracked gas logistics 1 that is rich in propylene and ethene at least in part, be separated into the logistics 2 of carbon three following cuts and the logistics 3 of carbon four above cuts after the cooling, described higher carbon number hydrocarbon catalytic pyrolysis unit is sent in logistics 3, make the logistics 3 of described carbon four above cuts be converted into the catalytically cracked gas logistics 6 that is rich in propylene and ethene at least in part, catalytically cracked gas logistics 6 is separated into the logistics 7 of carbon three following cuts and the logistics 8 of carbon four above cuts, the oxicracking system is sent in logistics 8, make the logistics 8 of described carbon four above cuts be converted into the oxicracking gas logistics 4 that is rich in ethene and propylene at least in part, the logistics 5 of carbon three following cuts will be isolated after logistics 4 coolings, with logistics 5, logistics 2 is sent into the oil scrubber that steam cracking device separates (recovery) system with logistics 7, in the splitting gas of water wash column or compressor, to improve the propylene and the ethylene yield of steam cracking device.
5. as the method for claim 2 or 4 described propylene enhancings and ethene, it is characterized in that, described catalytically cracked gas logistics 1 cooling back gas-liquid separation, obtain the logistics of carbon five following cuts and the logistics of carbon six above cuts, logistics with carbon five following cuts is separated into the logistics 2 of carbon three following cuts and the logistics of carbon four carbon five mixed fraction then, again with the logistics of carbon six above cuts and the logistics 3 that obtains carbon four above cuts after the logistics of carbon four carbon five mixed fraction mixes; Described oxicracking gas logistics 4 cooling back gas-liquid separations obtain the logistics of carbon six above cuts and the logistics of carbon five following cuts, isolate the logistics 5 of carbon three following cuts then from the logistics of carbon five following cuts; The described catalytically cracked gas logistics 6 cooling first gas-liquid separations in back obtain the logistics of carbon six above cuts and the logistics of carbon five following cuts, from the logistics of carbon five following cuts, isolate the logistics 7 of carbon three following cuts then, again with the logistics of carbon six above cuts and the logistics 8 that obtains carbon four above cuts after the logistics of carbon four carbon five mixed fraction mixes.
6. as the method for claim 1 or 3 described propylene enhancings and ethene, it is characterized in that, butane and the alkene mixture that described steam cracking process is produced sent into hydrogenation unit earlier, make the divinyl and the butine of the overwhelming majority in butane and the alkene mixture be converted into butylene, more described butane and alkene mixture are sent into described cracking c_4 treatment system.
7. as the method for claim 1 or 3 described propylene enhancings and ethene, it is characterized in that, the catalyzer that described oxicracking unit uses is conventional oxicracking catalyzer, for supporting the catalyzer of precious metal on the different carriers with regular or non-regular pore passage structure.
8. as the method for claim 1 or 3 described propylene enhancings and ethene, it is characterized in that, described method also is provided with carbon monoxide and removes the unit, before sending into steam cracking and tripping device, described cracking c_4 treatment system generation and isolated carbon three following cuts are admitted to carbon monoxide and remove the unit, to remove wherein most carbon monoxide or carbon monoxide is converted into carbonic acid gas.
9. as the method for claim 1 or 3 described propylene enhancings and ethene, it is characterized in that, described method also is provided with the acid gas removal unit, before sending into steam cracking and tripping device, described cracking c_4 treatment system produces and isolated carbon three following cuts are admitted to the acid gas removal unit, to remove wherein carbonic acid gas and other sour gas of the overwhelming majority.
10. as the method for claim 1 or 3 described propylene enhancings and ethene, it is characterized in that, described method also is provided with oxygen and removes the unit, before sending into steam cracking and tripping device, described cracking c_4 treatment system produces and isolated carbon three following cuts are admitted to oxygen and remove the unit and remove wherein most oxygen.
11. method as claim 1 or 3 described propylene enhancings and ethene, it is characterized in that, isolate the logistics of carbon five above cuts catalytically cracked gas that produces from described cracking c_4 treatment system and the oxicracking gas, with its recycle or deliver to the pyrolysis gasoline hydrogenation device.
12. the method as claim 1 or 3 described propylene enhancings and ethene is characterized in that, described catalytically cracked gas and oxicracking gas cool off with isolating temperature range be 0～100 ℃, preferred 0～40 ℃.
13. method as claim 1 or 3 described propylene enhancings and ethene, it is characterized in that the catalyzer that described carbon four catalytic pyrolysis unit and higher carbon number hydrocarbon catalytic pyrolysis unit use is one or more of modification or unmodified SAPO-34, ZSM-5, ZSM-11, ZSM-23, MCM-22, MCM-49, MCM-56 and 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, and used metal-salt is carbonate, vitriol, nitrate, oxalate, phosphoric acid salt, muriate or the corresponding ammonium salt of above-mentioned selected metal during modification.
14. the method as claim 1 or 3 described propylene enhancings and ethene is characterized in that the unitary temperature of reaction of described C _ 4 alkene catalytic pyrolysis is 400～600 ℃, 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 oxicracking is 500～900 ℃, and reaction pressure is 0.07～0.50MPa, and volume space velocity is 0.5～100h during liquid
-1, the charging mass ratio of oxygen and hydrocarbon raw material is 0.05～2; The unitary temperature of reaction of described higher carbon number hydrocarbon catalytic pyrolysis is 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.
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