CN102286297A - Method for increase production of propylene and ethylene - Google Patents
Method for increase production of propylene and ethylene Download PDFInfo
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- CN102286297A CN102286297A CN2010102043978A CN201010204397A CN102286297A CN 102286297 A CN102286297 A CN 102286297A CN 2010102043978 A CN2010102043978 A CN 2010102043978A CN 201010204397 A CN201010204397 A CN 201010204397A CN 102286297 A CN102286297 A CN 102286297A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- 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
Abstract
The invention relates to a method for increase production of propylene and ethylene in a steam pyrolyzing process. The steam pyrolyzing process comprises a pyrolyzing furnace and a separation (recovery) system, on this basis, a catalytic pyrolyzing system which takes catalytic pyrolyzing gasoline produced in an oil refining process as a raw material is additionally arranged, by the catalytic pyrolyzing system, the part or the whole of alkene of the catalytic pyrolyzing gasoline is converted into pyrolysis gas with rich propylene and ethylene, the catalytic pyrolysis gas is cooled and separated to form under-C5 fraction flow and over-C6 friction flow, the separation and the purification of the under-C5 fraction flow is completed by the separation (recovery) system in the steam pyrolyzing process, after the alkene content in the over-C6 fraction flow or in the mixture can be reduced by hydrogenation or naphthalizing, and other modes, then, the over-C6 friction flow is used as a pyrolysis raw material, and the defect of the insufficient pyrolysis raw material can be solved. In the invention, the potential of the separation (recovery) system in the steam pyrolyzing device can be utilized; as the catalytic pyrolyzing system formed by a catalytic pyrolyzing reactor and simple separation equipment is added, the production volume of light olefins such as the propylene, the ethylene and the like can be increased; and the economic benefit of enterprises can be increased.
Description
Technical field
The present invention relates to the method for a kind of propylene enhancing, ethene, more particularly, the present invention relates to a kind of method of utilizing existing preparing ethylene by steam cracking device and tripping device to improve propylene and ethylene yield.
Background technology
At present, the main mode of production of low-carbon alkene such as ethene, propylene is a steam cracking in the world, steam cracking process by pyrolyzer with separate (recovery) system two portions and constitute.In steam cracking process, cracking stock and water vapor mixture are heated to high temperature and carry out steam cracking reaction in pyrolyzer, the splitting gas of ethene, propylene is rich in generation, then this splitting gas is sent in separation (recovery) system to separate purification, 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 every year.For alleviating the disparities between supply and demand in state's inner propene, ethene market, fill up demand gap, China recent years has started second and third continuously and has taken turns the reconstruction and extension project of ethylene industry.Comprehensive various report, before 2010, the olefin plant of tens tame scales 80～1,200,000 tons of ethene/years will appear in China.In a foreseeable future, the imbalance between supply and demand in low-carbon alkene markets such as state's inner propene, ethene will be eased.It should be noted that, these scales all belong to traditional steam crack material at the employed cracking stock of olefin plant in 80～1,200,000 tons of ethene/years, such as petroleum naphtha, hydrogenation tail oil, lighter hydrocarbons etc., and supporting with it crude capacity does not obtain corresponding raising, may cause traditional cracking stock shortage or cracking stock quality to descend, thereby make separation (recovery) system in the steam cracking process in actual production, may have bigger operation surplus.Therefore, propylene, ethylene yield become an important factor that influences the business economic benefit in the steam cracking process to improve how to enlarge raw material sources.
Certain situation in the gasoline production process also merits attention: in the past few years, in order to protect environment, in the world wide motor spirit has been proposed higher index.Different with world other countries, the catalytically cracked gasoline that accounts for China's gasoline consumption 40% needs because its olefin(e) centent is higher to improve.A kind of way is that the temperature and the catalyst performance that improve catalytic cracking process reduce olefin(e) centent, and another kind of way is the catalytically cracked gasoline that has produced to be reduced the processing of olefin(e) centent.In conjunction with the composition of catalytically cracked gasoline and bibliographical information as can be known, to form in the olefins by catalytic cracking process of similar raw material with catalytically cracked gasoline, product comprises hydrogen, methane, ethane, ethene, propane, propylene, carbon four and carbon four above alkene paraffins mixture and a spot of aromatic hydrocarbons.As seen, the product of olefins in FCC gasoline catalytic cracking reaction form with steam cracking process in product form basically identical, can adopt with steam cracking process in (recoverys) system that separates separate purification and obtain propylene and ethylene product.Mainly be carbon six above paraffinic hydrocarbonss through remaining non-reacted parts behind the catalytic pyrolysis process in the catalytically cracked gasoline, form similar to petroleum naphtha, can mix cracking products such as to drop into pyrolyzer production ethene, propylene with petroleum naphtha, to solve the problem of pyrolyzer insufficient raw material.
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, descend or the cracking stock shortage causes the idle problem of production capacity at domestic cracking stock quality, proposed in existing steam cracking device, to increase system with the catalytically cracked gasoline preparing propylene by catalytic cracking of refinery and ethene to improve the method for propylene and ethylene yield.
Method provided by the invention, characteristics based on the product composition of the reaction of the olefins by catalytic cracking in the catalytically cracked gasoline that produces in the oil refining process and the product composition basically identical in the steam cracking process, advantage in conjunction with steam cracking process process and catalytic pyrolysis process, fully excavate the potentiality of separating (recovery) system in the existing steam cracking process, outside existing steam cracking process, increase a catalytic pyrolysis system, with the catalytically cracked gasoline that produces in the oil refining process is raw material, by catalytic cracking reaction carbon in the catalytically cracked gasoline four is rich in propylene to the olefin feed conversion generation of carbon nine, the catalytically cracked gas of ethene carries out forming carbon five following cut logistics and carbon six above cut logistics after the simple separation to catalytically cracked gas then; Carbon five following distillations are circulated separation (recovery) system in the steam cracking process to improve the output of propylene, ethene; The above distillations stream of carbon six reduced wherein by hydrogenation or with modes such as petroleum naphtha mix or the olefin(e) centent in the mixture after, it is fed steam cracking furnace produces propylene, ethene, to solve the insufficient problem of cracking stock.Can be the catalytic pyrolysis system of raw material with the catalytically cracked gasoline that produces in the oil refining process so just, to improve the output of propylene, ethene in the steam cracking process by increasing by one.
Concrete technical scheme is as follows:
The method of a kind of propylene enhancing and ethene, in steam cracking and tripping device thereof, increasing with the plant catalytic pressure gasoline is the catalytic pyrolysis system of raw material, said method comprising the steps of:
(1) catalytically cracked gasoline catalytic pyrolysis: the catalytically cracked gasoline of refinery is introduced the catalytic pyrolysis system, the alkene in the described raw material is converted at least in part the catalytically cracked gas that is rich in propylene and ethene;
(2) product reclaims: the catalytically cracked gas that step (1) is obtained separates, obtain carbon five following cut logistics and carbon six above cut logistics, the logistics of isolated carbon five following cuts is sent in the oil scrubber or water wash column splitting gas of steam cracking and tripping device thereof;
(3) reduce olefin(e) centent: the carbon six above distillations streams that step (2) is obtained reduce olefin(e) centent by hydrogenation or with the petroleum naphtha hybrid mode, send into steam cracking furnace as cracking stock, are used to produce the low-carbon alkene product that comprises ethene and propylene.
Preferably, in described olefins by catalytic cracking unit, alkene in the described plant catalytic pressure gasoline raw material is converted into the catalytically cracked gas logistics 1 that is rich in propylene and ethene at least in part, catalytically cracked gas logistics 1 cooling and through separating, obtain the logistics 2 of carbon five following cuts and the logistics 3 of carbon six above cuts, the logistics 3 of carbon five following cuts is sent in the oil scrubber or water wash column splitting gas of steam cracking and tripping device thereof, with the propylene of raising steam cracking device and the output of ethene.
More preferably, the logistics 3 of described carbon six above cuts reduces olefin(e) centent by hydrogenation or with the petroleum naphtha hybrid mode, drops into steam cracking furnace as cracking stock then, comprises the low-carbon alkene product of ethene and propylene with production.
For carbon six above cut fraction hydrogenation or with the blending ratio of petroleum naphtha, decide on the olefin(e) centent in the mixture, further preferably, the logistics 3 of described carbon six above cuts is controlled at olefin(e) centent below 1% by hydrogenation or with the petroleum naphtha hybrid mode, drops into steam cracking furnace as cracking stock then.Olefin(e) centent is higher, and cracking furnace coking speed is higher, and the cycle of operation can shorten.
Preferably, catalytically cracked gas cool off with isolating temperature range be 0～100 ℃, preferred 0～40 ℃.
Preferably, the catalyzer that described catalytic pyrolysis system uses is one or more of modification or unmodified SAPO-34, ZSM-5, ZSM-11, ZSM-23, MCM-22, MCM-49, MCM-56 and mordenite, modifying element comprises one or more in phosphorus, lanthanum, cerium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, cadmium, zirconium, molybdenum, tungsten and the aluminium, and used metal-salt is carbonate, vitriol, nitrate, oxalate, phosphoric acid salt or muriate or the corresponding ammonium salt of above-mentioned selected metal during modification.
Preferably, the temperature of reaction of described catalytic pyrolysis is 400～600 ℃, and reaction pressure is 0.07～0.50MPa, and volume space velocity is 0.5～100h during liquid
-1, water vapour and catalytic pyrolysis material feeding mass ratio are 0～10.
Preferably, described plant catalytic pressure gasoline consists of paraffinic hydrocarbons, monoolefine, a spot of naphthenic hydrocarbon and a spot of aromatic hydrocarbons.
Preferably, described catalytically cracked gasoline introducing amount need be determined according to the ability to bear of steam heat cracking steam cracking separation system.
The pyrolyzer of the present invention in existing steam cracking process process with separate (recovery) system outside, increasing by one is the catalytic pyrolysis system of raw material with the catalytically cracked gasoline that produces in the oil refining process, with the catalytically cracked gasoline is raw material, making it alkene by catalytic cracking reaction partly changes into and has been rich in propylene, the catalytically cracked gas of ethene, the catalytically cracked gas refrigerated separation is formed carbon five following cut logistics and carbon six above cut logistics, and the separation of the carbon five following cut logistics in this catalytically cracked gas purification is finished by the separation in the steam cracking process (recovery) system, and carbon six above cut logistics then reduce wherein by hydrogenation or with modes such as petroleum naphtha mix or the olefin(e) centent in the mixture is used as cracking stock.Only needing to increase the catalytic pyrolysis system that the catalytically cracked gasoline that produces in the oil refining process is a raw material in existing steam cracking process, is a kind of practicable method that improves propylene, ethylene yield in the existing steam cracking process.
With the catalytically cracked gasoline that produces in the oil refining process is the catalytic pyrolysis system of raw material, and the catalytic cracking reaction device is to be made of the olefins by catalytic cracking reactor.The catalytic cracking reaction device can be one or more combination in fixed bed, moving-bed, the fluidized-bed.Raw material in the catalytic pyrolysis system is the catalytically cracked gasoline that produces in the oil refining process.Catalytically cracked gasoline mainly consists of paraffinic hydrocarbons, alkene (monoolefine) and a spot of naphthenic hydrocarbon and the aromatic hydrocarbons of carbon more than five.
The catalyzer that described catalytic pyrolysis system uses is one or more of modification or unmodified SAPO-34, ZSM-5, ZSM-11, ZSM-23, MCM-22, MCM-49, MCM-56 and mordenite.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 and ethene that is converted into of the alkene component in this patent raw material.Olefins by catalytic cracking catalyst reaction temperatures scope is 400～600 ℃, and reaction pressure (gauge pressure) scope is 0.07～0.50MPa, and water and weight of material ratio are 0～10, and material charging air speed scope is 0.5～100h
-1
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, adding with the catalytically cracked gasoline that produces in the oil refining process in steam cracking process is in the catalytic pyrolysis system of raw material, catalytic pyrolysis product in this catalytic pyrolysis system is carried out initial gross separation form carbon five following cut logistics and carbon six above cut logistics, and with the circulate corresponding position of separation (recovery) system in the steam cracking process of carbon five following distillations, the above distillations stream of carbon six reduced wherein by hydrogenation or with modes such as petroleum naphtha mix or the content in the mixture after as cracking stock, not only solve the cracking stock shortage problem, also can improve propylene and ethylene yield, increase economic benefit of enterprises.
Embodiment
Further describe the present invention below in conjunction with embodiment.Scope of the present invention is not limited by embodiment.
Comparative example 1
The olefin plant of certain 1,000,000 tons of/year ethene has 11 pyrolyzer, and wherein 6 is the light oil cracking stove, 3 heavy oit pyrolysis stoves, and 1 is the lighter hydrocarbons pyrolyzer, one is standby pyrolyzer.The light oil cracking stove is based on naphtha cracking, and the heavy oit pyrolysis stove is cracked into the master with hydrogenation tail oil, and the lighter hydrocarbons pyrolyzer is cracked into the master with cycle ethane and propane.Each pyrolyzer charging capacity sees Table 1, and ethene, propylene, butane butylene yield and output see Table 2.
1,000,000 tons of olefin plant cracking stock years of table 1 are thrown oil mass
| Raw material | Petroleum naphtha | HVGO | Cycle ethane | Recycled propane |
| Charging capacity, ten thousand tons/year | 228.00 | 90.00 | 19.35 | 2.66 |
Table 2 1,000,000 tons of olefin plant primary products yield and output
| Ultimate production, ten thousand tons/year | Total recovery, wt% | |
| Ethene | 100.262 | 30.97 |
| Propylene | 50.722 | 15.67 |
By table 1 and table 2 as can be known, these cracking stocks generate mixed pyrolysis gas through pyrolyzer thermo-crackings,
Mixed pyrolysis gas is through after separating the separation purification of (recovery) system, 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%;
Embodiment 1
On the basis of comparative example 1, increasing by one is the catalytic pyrolysis system of raw material (the raw material composition sees Table 3) with the catalytically cracked gasoline, and the amount of finish of the pressure gasoline of this catalytic pyrolysis system is 50,000 tons/year, and particular flow sheet is shown in Figure of description.
Table 3 catalytically cracked gasoline is formed
(1) earlier catalytically cracked gasoline is fed in the catalytic cracking reaction device 1, the alkene of this catalytically cracked gasoline and specific catalyst 1 contact reacts, this olefins by catalytic cracking catalyzer is with phosphorus and/or alkali-earth metal modified little crystal grain (particle diameter is less than 800nm) ZSM-5 molecular sieve type catalyst, (silica alumina ratio is 100 for consisting of of catalyzer: 5wt%P, 1wt%La, 64wt%ZSM-5 molecular sieve, particle diameter is 500nm), the 30wt% silicon oxide, produce by the Beijing Chemical Research Institute.Be 0.5 in 550 ℃ of temperature of reaction, reaction pressure (gauge pressure) 0.1MPa, water-oil ratio, air speed is 5h
-1Condition under, catalyzer 1 becomes to be rich in the logistics 1 of propylene, ethene with the alkene part catalytic pyrolysis in the charging, wherein propylene content is 15% in the logistics 1, ethylene content is 5%.
(2) logistics 1 cooling is separated, logistics 2 is carbon five and carbon five following components, and logistics 3 is for containing the carbon six above components of part carbon five.Ethylene content is 15.9% in the logistics 2, and propylene content is 47.7%, and olefin(e) centent is 19.65% in the logistics 3.
(3) be controlled at logistics 2 temperature in 240 ℃ of scopes, pressure is greater than under the 0.7MPa condition, feed in the splitting gas pipeline of oil scrubber of separation (recovery) system in the steam cracking industry.
(4) with logistics 3 with after at least 20 times petroleum naphtha mixes, can be used as steam crack material, it is fed in the pyrolyzer in steam cracking process and is used to produce cracking products such as ethene, propylene.
According to the calculation of yield of above process, after the catalytic pyrolysis system that increases with the catalytically cracked gasoline raw material, the propene yield of catalytically cracked gasoline reaches 15%, and yield of ethene reaches 5%.Catalytically cracked gas is separated, and the following components of carbon five is fed in the splitting gas pipeline of oil scrubber of separation (recovery) system in the steam cracking process, but thus every year 0.25 ten thousand ton of increasing output of ethylene, propylene increases production 0.75 ten thousand ton; The isolating carbon six above cuts based on alkane of catalytic pyrolysis system are mixed as cracking stock with petroleum naphtha, thereby solve the steam cracking problem of shortage.
This shows, in original steam cracking process process, increase is the catalytic pyrolysis system of raw material with the catalytically cracked gasoline that produces in the oil refining process, under the situation that increases a small amount of catalytic cracking reaction device, full factory's ethene and productivity of propylene are improved, steam crack material shortage situation is taken on a new look to some extent, helps enterprise and increases economic efficiency.
Claims (9)
1. the method for propylene enhancing and ethene is characterized in that, in steam cracking and tripping device thereof, increasing with the plant catalytic pressure gasoline is the catalytic pyrolysis system of raw material, said method comprising the steps of:
(1) catalytically cracked gasoline catalytic pyrolysis: the catalytically cracked gasoline of refinery is introduced the catalytic pyrolysis system, the alkene in the described raw material is converted at least in part the catalytically cracked gas that is rich in propylene and ethene;
(2) product reclaims: the catalytically cracked gas that step (1) is obtained separates, obtain carbon five following cut logistics and carbon six above cut logistics, the logistics of isolated carbon five following cuts is sent in the oil scrubber or water wash column splitting gas of steam cracking and tripping device thereof;
(3) reduce olefin(e) centent: the carbon six above distillations streams that step (2) is obtained reduce olefin(e) centent by hydrogenation or with the petroleum naphtha hybrid mode, send into steam cracking furnace as cracking stock, are used to produce the low-carbon alkene product that comprises ethene and propylene.
2. the method for propylene enhancing as claimed in claim 1 and ethene, it is characterized in that, in described olefins by catalytic cracking unit, alkene in the described plant catalytic pressure gasoline raw material is converted into the catalytically cracked gas logistics 1 that is rich in propylene and ethene at least in part, catalytically cracked gas logistics 1 cooling and through separating, obtain the logistics 2 of carbon five following cuts and the logistics 3 of carbon six above cuts, the logistics 3 of carbon five following cuts is sent in the oil scrubber or water wash column splitting gas of steam cracking and tripping device thereof, with the propylene of raising steam cracking device and the output of ethene.
3. the method for propylene enhancing as claimed in claim 2 and ethene, it is characterized in that, the logistics 3 of described carbon six above cuts reduces olefin(e) centent by hydrogenation or with the petroleum naphtha hybrid mode, drop into steam cracking furnace as cracking stock then, comprise the low-carbon alkene product of ethene and propylene with production.
4. the method for propylene enhancing as claimed in claim 3 and ethene is characterized in that, the logistics 3 of described carbon six above cuts is controlled at olefin(e) centent below 1% by hydrogenation or with the petroleum naphtha hybrid mode, drops into steam cracking furnace as cracking stock then.
5. the method for propylene enhancing as claimed in claim 2 and ethene is characterized in that, catalytically cracked gas cool off with isolating temperature range be 0～100 ℃.
6. the method for propylene enhancing as claimed in claim 2 and ethene is characterized in that, catalytically cracked gas cool off with isolating temperature range be 0～40 ℃.
7. the method for propylene enhancing as claimed in claim 1 and ethene, it is characterized in that, the catalyzer that described catalytic pyrolysis system uses is 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.
8. the method for propylene enhancing as claimed in claim 1 and ethene is characterized in that, the temperature of reaction of described catalytic pyrolysis is 400～600 ℃, and reaction pressure is 0.07～0.50MPa, and volume space velocity is 0.5～100h during liquid
-1, water vapour and catalytic pyrolysis material feeding mass ratio are 0～10.
9. the method for propylene enhancing as claimed in claim 1 and ethene is characterized in that, described plant catalytic pressure gasoline contains paraffinic hydrocarbons, monoolefine, naphthenic hydrocarbon and aromatic hydrocarbons.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104250197A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Butadiene preparation method |
| CN109422608A (en) * | 2017-09-04 | 2019-03-05 | 中国石油化工股份有限公司 | The preparation method of ethylene |
| CN111826198A (en) * | 2020-07-28 | 2020-10-27 | 山东京博石油化工有限公司 | Method for combining catalytic cracking and gasoline hydrogenation |
| CN114456025A (en) * | 2020-10-21 | 2022-05-10 | 中国石油化工股份有限公司 | Method and system for producing ethylene and propylene by catalyzing light gasoline |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104250197A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Butadiene preparation method |
| CN109422608A (en) * | 2017-09-04 | 2019-03-05 | 中国石油化工股份有限公司 | The preparation method of ethylene |
| CN109422608B (en) * | 2017-09-04 | 2022-08-12 | 中国石油化工股份有限公司 | Process for the preparation of ethylene |
| CN111826198A (en) * | 2020-07-28 | 2020-10-27 | 山东京博石油化工有限公司 | Method for combining catalytic cracking and gasoline hydrogenation |
| CN114456025A (en) * | 2020-10-21 | 2022-05-10 | 中国石油化工股份有限公司 | Method and system for producing ethylene and propylene by catalyzing light gasoline |
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