CN102285857A - Method for increasing yields of propylene and ethylene - Google Patents
Method for increasing yields of propylene and ethylene Download PDFInfo
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Abstract
The invention relates to a method for increasing yields of propylene and ethylene in a steam cracking process. A cracking furnace and a separation system are provided in a steam cracking process, and a catalytic cracking system is additionally arranged on that basis, wherein the catalytic cracking system takes a C4 fraction generated in an oil refining process as a raw material; and a mixture of C4 olefin and alkane is converted to respectively obtain a below C3 material flow rich in the propylene and the ethylene and a material flow rich in over C4 alkane through the catalytic cracking system, wherein the below C3 material flow is subject to followed separation and purification treatment in the separation (recovery) system in a steam cracking device, and the material flow rich in over C4 alkane is fed into the steam cracking device and is taken as a qualified cracking raw material. The invention is characterized in that: the potential of the separation (recovery) system in the steam cracking process is fully tapped, a range of a raw material of the steam cracking process is extended, and a catalytic cracking system, consisting of a catalytic cracking reactor and a simple separating device, is additionally provided only, thus the refinery C4 is converted into the cracking raw material including light olefin such as the propylene, the ethylene and the like, the C4 alkane and the like, and the economic benefit of corporation is beneficial to being improved.
Description
Technical field
The present invention relates to the method for a kind of propylene enhancing, ethene, more particularly, the present invention relates to a kind of method of utilizing existing preparing ethylene by steam cracking device and separation system thereof to improve propylene and ethylene yield.
Background technology
At present, the main mode of production of low-carbon alkene such as ethene, propylene is steam cracking (thermo-cracking) in the world, this technology by pyrolyzer with separate (recovery) system two portions and constitute.In steam cracking process, the mixture of cracking stock and water vapor is heated to high temperature and carries out heat scission reaction in pyrolyzer, the splitting gas of ethene and propylene is rich in generation, then this splitting gas is sent in separation (recovery) system to separate purification, obtained cracking products such as ethene, propylene.
In recent years, quick growth along with domestic economy, the market requirement of low-carbon alkene such as ethene, propylene is increasing, and domestic ethene, the original throughput of propylene can not satisfy the market requirement that increases rapidly, so China all wants a large amount of ethene of import, propylene and downstream derivative thereof every year.For alleviating the disparities between supply and demand in state's inner propene, ethene market, fill up demand gap, China recent years has started second, third continuously and has taken turns the reconstruction and extension project of ethylene industry.Comprehensive various report, to 2010, China built up or the ethylene unit of annual output 80～1200000 of building ton ethene scale reach ten surplus family, the imbalance between supply and demand in low-carbon alkene markets such as state's inner propene, ethene will be alleviated gradually.It should be noted that, the employed cracking stock of above-mentioned ethylene unit all belongs to traditional steam crack material, such as petroleum naphtha, hydrogenation tail oil, lighter hydrocarbons etc., but supporting with it crude capacity does not but obtain corresponding raising, be difficult to traditional cracking of ethylene raw material of providing enough, thereby will cause traditional cracking stock shortage and quality thereof to descend, make that may there be bigger operation surplus in separation (recovery) system in the steam cracking process in actual production.Therefore, how to enlarge raw material sources and become an important factor that influences the business economic benefit with propylene and ethylene yield in the raising steam cracking process.
Refinery casing head is mainly from catalytic cracking unit (FCC), though also by-product C-4-fraction such as viscosity breaking, thermally splitting and coking, comparatively small amt.Catalytic cracking unit by-product C-4-fraction is different because of cracking level and catalyzer again, is generally 9～12% of fresh feed, does not contain divinyl (perhaps content is very little) in its cut, and the butylene massfraction is about 50%, and all the other are butane.The utilization of China's refinery's C-4-fraction is general to divide two kinds, i.e. direct industrial utilization and separate chemical utilization afterwards.Directly industrial utilization comprise without processing directly act as a fuel the liquefied petroleum gas (LPG) used, mix the gasoline steam regulation and press, directly do fuel gas and use and generate gasoline alkylate, methyl tertiary butyl ether liquid fuel various ways such as (MTBE) through chemical process, wherein the added value high product is gasoline alkylate and MTBE, but they can cause damage to environment in manufacturing and use.In environment protection task urgent today, it has not been the future thrust of carbon four utilization of resources technology that this class is utilized approach.And because the existence of a large amount of alkene in the component, refinery's C-4-fraction also can't directly be used as the cracker raw material.Separating the back chemical utilization is that each main ingredient in refinery's C-4-fraction is separated, made with extra care, and is used as the raw material of production downstream Chemicals then.Because the boiling point and the zero pour of each component are very close in refinery's C-4-fraction, the relative volatility difference of some component is minimum, adopt common distillating method to be difficult to effective separation, if adopt low temperature crystallization to separate, energy expenditure will be very considerable, and these two kinds of separation methods all are difficult to guarantee the purity of separated portion, also will carry out follow-up refinement treatment, so the separation tooling cost of C-4-fraction is higher.This shows, how could under the prerequisite of environmental protection, realize its high value added utilization, become the problem that present refinery one factory presses for solution at the C-4-fraction that refinery produces.
At above-mentioned situation, each big petro-chemical corporation drops into strength one after another and develops technology and the catalyzer that carbon four low value alkene alkane are produced low-carbon alkenes such as ethene, propylene in the world, and has obtained satisfied result.By Chinese patent CN1915933A as can be known, in C 4 olefin and paraffins mixture catalytic pyrolysis process, product mainly is hydrogen, methane, carbon two, carbon three, carbon four, all the other are C5～C12 chain type alkane and the following aromatic hydrocarbons of alkene and 1% (weight), and the product in these products and the steam cracking process is formed basically identical.In addition, in the catalytic pyrolysis process at a lower temperature, the speed of reaction of alkane is far below alkene.Therefore, when alkane and alkene mixture through behind the catalytic cracking reaction, in the product with enrichment alkane, and carbon four and above a kind of just fine steam crack material of alkane.
Summary of the invention
The present invention is in order to alleviate the imbalance between supply and demand in low-carbon alkene markets such as state's inner propene and ethene, enlarge the raw material sources of steam cracking and tripping device, proposed in existing steam cracking device, to increase the system of refinery's C-4-fraction preparing propylene by catalytic cracking and ethene to improve the method for propylene and ethylene yield.
Method provided by the invention, based on the product of the catalytic cracking reaction of the C-4-fraction that produces in the oil refining process form with steam cracking process in product form the characteristics of basically identical, advantage in conjunction with steam cracking process process and catalytic pyrolysis process, fully excavate in the existing steam cracking process and separate the potentiality of (recovery) system, and effectively enlarged the source of steam crack material.The present invention increases a catalytic pyrolysis system outside existing steam cracking process, with the C-4-fraction that produces in the oil refining process is to be rich in low-carbon alkenes such as propylene and ethene in the catalytically cracked gas that generates of feedstock conversion, and the light paraffins based on butane passes through catalytic cracking reaction and enrichment simultaneously.The Separation ﹠ Purification of propylene and low-carbon alkene products such as ethene by separating in original steam cracking process (recovery) system finish, made full use of the operation surplus of separation (recovery) system, light paraffins is then sent into the high quality raw material of pyrolyzer as steam cracking.So just can be by increasing a catalytic pyrolysis system that is raw material with the C 4 olefin that produces in the oil refining process and paraffins mixture, to improve the output of propylene and ethene in the steam cracking process.
Concrete technical scheme is as follows:
The method of propylene enhancing provided by the invention and ethene is characterized in that, in steam cracking and tripping device thereof, increasing with refinery's C-4-fraction is the catalytic pyrolysis system of raw material, said method comprising the steps of:
(1) refinery C four catalytic pyrolysiss: butane and C 4 olefin cut that refinery produces are introduced the catalytic pyrolysis system, described raw material is converted at least in part the catalytically cracked gas that is rich in propylene and ethene;
(2) product is sent into steam cracking device: the catalytically cracked gas that step (1) is obtained separates, obtain carbon three following fraction A 1 and carbon four above fraction B 1, carbon three following fraction A 1 are sent in the splitting gas of oil scrubber, water wash column or compressor of steam cracking and tripping device thereof, and carbon four above fraction B 1 are sent into the cracking stock feed system, with the propylene that improves steam cracking device and the output of ethene.
Preferably, set up mixed olefins and alkane catalytic pyrolysis unit in described catalytic pyrolysis system, step (2) is separated the carbon four above fraction B 1 that obtain send into described mixed olefins and alkane catalytic pyrolysis unit, described carbon four above fraction B 1 are converted into the catalytically cracked gas logistics that is rich in propylene and ethene at least in part, through cooling off and separating, obtain carbon three following fraction A 2 and carbon four above fraction B 2, send into the oil scrubber of steam cracking and tripping device thereof after carbon three following fraction A 1 and carbon three following fraction A 2 are converged, in the splitting gas of water wash column or compressor, carbon four above fraction B 2 are sent into the pyrolyzer feed system, as the raw material of preparing ethylene by steam cracking.
Preferably, described catalytically cracked gas cool off with isolating temperature range be 0～100 ℃, preferred 0～40 ℃.
Preferably, the catalyzer that refinery C four catalytic pyrolysis unit and mixed olefins and alkane catalytic pyrolysis unit use in the described catalytic pyrolysis system is modification or unmodified SAPO-34, ZSM-5, ZSM-11, ZSM-23, MCM-22, MCM-49, one or more of MCM-56 and mordenite, modifying element comprises phosphorus, lanthanum, cerium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, cadmium, zirconium, molybdenum, in tungsten and the aluminium one or more, used metal-salt is the carbonate of above-mentioned selected metal during modification, vitriol, nitrate, oxalate, phosphoric acid salt or muriate or corresponding ammonium salt.
Preferably, the temperature of reaction of described refinery C four catalytic pyrolysiss is 400～600 ℃, and reaction pressure is 0.07～0.50MPa, and volume space velocity is 0.5～100h during liquid
-1, water vapour and catalytic pyrolysis material feeding mass ratio are 0～10; Described mixed olefins and the unitary temperature of reaction of alkane catalytic pyrolysis are 450～650 ℃, and reaction pressure is 0.07～0.50MPa, and volume space velocity is 0.5～100h during liquid
-1, water vapour and catalytic pyrolysis material feeding mass ratio are 0～10.
The pyrolyzer of the present invention in existing steam cracking process process with separate (recovery) system outside, increase a catalytic pyrolysis system that is raw material with the C 4 olefin that produces in the oil refining process and paraffins mixture, make it partly to change into the catalytically cracked gas that is rich in propylene and ethene by making up different catalyzed reactions, and carbon three is finished by the separation in the steam cracking process (recovery) system with the separation purification of lower section in this catalytically cracked gas, carbon four is sent into steam cracking device as the high-quality cracking stock with top, only needing to increase the catalytic pyrolysis system that a C 4 olefin that produces in oil refining process and paraffins mixture are raw material in existing steam cracking process, is to improve propylene in the existing steam cracking process, a kind of practicable method of ethylene yield.
The catalytic pyrolysis system that is raw material with the C 4 olefin that produces in the oil refining process and paraffins mixture comprises two class catalytic cracking reaction devices: i.e. C _ 4 alkene catalytic pyrolysis reactor, mixed olefins and alkane catalytic cracking reaction device.Reactor types can be one or more combination in fixed bed, moving-bed, the fluidized-bed.
The C _ 4 alkene catalytic pyrolysis catalyzer can be 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 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.C _ 4 alkene catalytic pyrolysis catalyst reaction temperatures scope is 400～600 ℃, and reaction pressure (gauge pressure) scope is 0.07～0.50MPa, and water and weight of material ratio are 0～10, and material charging air speed scope is 0.5～100h
-1
Mixed olefins and alkane catalytic cracking catalyst can be 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.Mixed olefins and alkane catalytic cracking catalyst can be converted into the catalytically cracked gas that is rich in propylene, ethene at least in part with the carbon in the catalytic pyrolysis raw material four to carbon nine alkene and paraffins mixture.Mixed olefins and the unitary temperature of reaction of alkane catalytic pyrolysis are 450～650 ℃, and reaction pressure is 0.07～0.50MPa, and volume space velocity is 0.5～100h during liquid
-1, water vapour and catalytic pyrolysis material feeding mass ratio are 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.
In sum, in steam cracking process, add the catalytic pyrolysis system that is raw material with the C 4 olefin that produces in the oil refining process and paraffins mixture, catalytic pyrolysis product in this catalytic pyrolysis system is carried out initial gross separation, separation (recovery) system that isolating product partly enters in the steam cracking process obtains ethene, propylene, part enters pyrolyzer circulation cracking, thereby improved propylene and ethylene yield, increased economic benefit of enterprises.
Embodiment
Further describe the present invention below in conjunction with embodiment.Scope of the present invention is not limited by these embodiment.
Comparative example 1
Certain refinery one factory has and produces 1000000 tons of ethylene units per year, has 11 pyrolyzer, and wherein 6 is the light oil cracking stove, 3 heavy oit pyrolysis stoves, and 1 is the lighter hydrocarbons pyrolyzer, one is standby pyrolyzer.The light oil cracking stove is based on naphtha cracking, and the heavy oit pyrolysis stove is cracked into the master with hydrogenation tail oil, and the lighter hydrocarbons pyrolyzer is cracked into the master with cycle ethane and propane.Each pyrolyzer charging capacity sees Table 1, and ethene, propylene, butane butylene yield and output see Table 2.
1,000,000 tons of olefin plant cracking stock years of table 1 are thrown oil mass
| Raw material | Petroleum naphtha | 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 |
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%;
The main component of refinery's C-4-fraction that refinery produces in this refinery one factory is as shown in table 3:
The main component of table 3 refinery C-4-fraction
| Component | Trimethylmethane | Normal butane | Iso-butylene | 1-butylene | 2-butylene |
| Content wt% | 34 | 10 | 15 | 13 | 28 |
Embodiment 1
On the basis of comparative example 1, increasing by one is the catalytic pyrolysis system of raw material with C 4 olefin in the oil refining process and paraffins mixture, and refinery C four treatment capacities of this system are 100,000 tons/year.Shown in patent accompanying drawing, this catalytic pyrolysis system mainly is made up of C _ 4 alkene catalytic pyrolysis reactor, mixed olefins and alkane catalytic cracking reaction device, and is specific as follows:
(1) at first the butane that provides in the oil refining process and butene mixture are fed in catalytic cracking reaction device 1 (the olefins by catalytic cracking reactor), the C 4 olefin in the raw material contacts with alkene catalyst and is 3h in 550 ℃ of temperature of reaction, reaction pressure (gauge pressure) 0.15MPa, air speed
-1Carry out catalytic cracking reaction under the condition, this catalyzer becomes to be rich in the logistics 1 of propylene and ethene with 70% C _ 4 alkene catalytic pyrolysis in the charging, and wherein propylene content is 17.9% in the logistics 1, and ethylene content is 5.6%.This olefins by catalytic cracking catalyzer is with phosphorus and/or alkali-earth metal modified little crystal grain (particle diameter is less than 800nm) ZSM-5 molecular sieve type catalyst, (silica alumina ratio is 100 for consisting of of catalyzer: 5wt%P, 2wt%La, 64wt%ZSM-5 molecular sieve, particle diameter is 500nm), the 29wt% silicon oxide, produce by the Beijing Chemical Research Institute.
(2) logistics 1 is cooled to 20 ℃, separates, obtain logistics 2 and logistics 3, wherein logistics 2 is carbon five following components, and logistics 3 is for containing the carbon six above components of small amount of carbon five.
(3) separate in the rectifying tower that logistics 2 is fed in this catalytic pyrolysis system, obtain logistics 4 and logistics 5, logistics 4 is carbon three following components, and logistics 5 is carbon four carbon pentaene hydrocarbon paraffins mixtures.
(4) logistics 3 is mixed with logistics 5, obtain logistics 6, logistics 6 is composed as follows:
1) have neither part nor lot in the butane of reaction, its content is 59.9%;
2) unreacted C 4 olefin, its content are 22.9%;
3) content be 11.0% transform the alkene (mainly being that carbon five is to carbon eight) form by C 4 olefin;
4) carbon five is to carbon eight alkane, and its content is 5.2%;
5) aromatic hydrocarbons, its content are 1%.
(5) logistics 6 is fed in catalytic cracking reaction device 2 (mixed olefins and the alkane catalytic cracking reaction devices).In catalytic cracking reaction device 2, logistics 6 contacts with alkane olefin cracking catalyzer with mixed olefins and is 3 hours in 600 ℃ of temperature of reaction, reaction pressure (gauge pressure) 0.10MPa, air speed
-1Condition under carry out catalytic cracking reaction, this catalyzer becomes to be rich in the logistics 7 of propylene, ethene with most of carbon four in the logistics 6 to carbon eight olefins by catalytic cracking, wherein propylene content is 12.1% in the logistics 7, ethylene content is 3.9%.Consisting of of this catalyzer: 4wt%P, 3wt%La, 2wt%Ca, 2wt%Ag, 60wt%ZSM-5 molecular sieve (silica alumina ratio is 140, and particle diameter is 400 nanometers), 29wt% silicon oxide are produced by the Beijing Chemical Research Institute.
(6) with logistics 7 through being cooled to 20 ℃, obtain logistics 8 and logistics 9, logistics 8 is carbon five following components, logistics 9 is for containing the carbon six above components of small amount of carbon five.
(7) with separating in the rectifying tower in the logistics 8 catalytic pyrolysis systems, obtain logistics 10 and logistics 11, logistics 10 carbon three following components wherein, logistics 11 is carbon four C 5 alkane components, the inside contains small amounts of olefins.
(8) logistics 11 is fed the pyrolyzer feed circuit, enter pyrolyzer as cracking stock, the yield of ethene of this material in steam cracking reaction is 32%, and propene yield is 15%.
(9) logistics 10 and logistics 4 mixed after, with its temperature be controlled in 240 ℃ of scopes, pressure is greater than under the 0.7MPa condition, feed in separation (recovery) system of steam cracking process in the splitting gas pipeline in the oil scrubber.
Calculation result shows that after increasing a catalytic pyrolysis system that is raw material with the C 4 olefin and the paraffins mixture of refinery generation, the annual propylene enhancing of factory is 3.5 ten thousand tons entirely, 2.4 ten thousand tons of the annual increasing output of ethylene of full factory.
This shows, in original steam cracking process process, the catalytic pyrolysis system that increase is raw material with the C 4 olefin that produces in the oil refining process and paraffins mixture, under the situation that increases a small amount of catalytic cracking reaction device and simple separating unit, full factory's ethene and propone output are significantly improved, and help enterprise and increase economic efficiency.
Claims (6)
1. the method for propylene enhancing and ethene is characterized in that, in steam cracking and tripping device thereof, increasing with refinery's C-4-fraction is the catalytic pyrolysis system of raw material, said method comprising the steps of:
(1) refinery C four catalytic pyrolysiss: butane and C 4 olefin cut that refinery produces are introduced the catalytic pyrolysis system, described raw material is converted at least in part the catalytically cracked gas that is rich in propylene and ethene;
(2) product is sent into steam cracking device: the catalytically cracked gas that step (1) is obtained separates, obtain carbon three following fraction A 1 and carbon four above fraction B 1, carbon three following fraction A 1 are sent in the splitting gas of oil scrubber, water wash column or compressor of steam cracking and tripping device thereof, and carbon four above fraction B 1 are sent into the cracking stock feed system, with the propylene that improves steam cracking device and the output of ethene.
2. the method for propylene enhancing as claimed in claim 1 and ethene, it is characterized in that, set up mixed olefins and alkane catalytic pyrolysis unit in described catalytic pyrolysis system, step (2) is separated the carbon four above fraction B 1 that obtain send into described mixed olefins and alkane catalytic pyrolysis unit, described carbon four above fraction B 1 are converted into the catalytically cracked gas logistics that is rich in propylene and ethene at least in part, through cooling off and separating, obtain carbon three following fraction A 2 and carbon four above fraction B 2, send into the oil scrubber of steam cracking and tripping device thereof after carbon three following fraction A 1 and carbon three following fraction A 2 are converged, in the splitting gas of water wash column or compressor, carbon four above fraction B 2 are sent into the pyrolyzer feed system, as the raw material of preparing ethylene by steam cracking.
3. the method for propylene enhancing as claimed in claim 3 and ethene is characterized in that, described catalytically cracked gas cool off with isolating temperature range be 0～100 ℃.
4. the method for propylene enhancing as claimed in claim 3 and ethene is characterized in that, described catalytically cracked gas cool off with isolating temperature range be 0～40 ℃.
5. the method for propylene enhancing as claimed in claim 3 and ethene, it is characterized in that, the catalyzer that refinery C four catalytic pyrolysis unit and mixed olefins and alkane catalytic pyrolysis unit use in the described catalytic pyrolysis system is modification or unmodified SAPO-34, ZSM-5, ZSM-11, ZSM-23, MCM-22, MCM-49, one or more of MCM-56 and mordenite, modifying element comprises phosphorus, lanthanum, cerium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, cadmium, zirconium, molybdenum, in tungsten and the aluminium one or more, used metal-salt is the carbonate of above-mentioned selected metal during modification, vitriol, nitrate, oxalate, phosphoric acid salt or muriate or corresponding ammonium salt.
6. the method for propylene enhancing as claimed in claim 3 and ethene is characterized in that, the temperature of reaction of described refinery C four catalytic pyrolysiss is 400～600 ℃, and reaction pressure is 0.07～0.50MPa, and volume space velocity is 0.5～100h during liquid
-1, water vapour and catalytic pyrolysis material feeding mass ratio are 0～10; Described mixed olefins and the unitary temperature of reaction of alkane catalytic pyrolysis are 450～650 ℃, and reaction pressure is 0.07～0.50MPa, and volume space velocity is 0.5～100h during liquid
-1, water vapour and catalytic pyrolysis material feeding mass ratio are 0～10.
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| CN113620768A (en) * | 2020-05-08 | 2021-11-09 | 中国石油化工股份有限公司 | Method for producing ethylene, propylene and aromatic hydrocarbon and catalytic reaction system |
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| CN113620768B (en) * | 2020-05-08 | 2024-02-09 | 中国石油化工股份有限公司 | Method for producing ethylene, propylene and aromatic hydrocarbon and catalytic reaction system |
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