CN102285851B - Method for increasing yields of ethylene and propylene - Google Patents
Method for increasing yields of ethylene and propylene Download PDFInfo
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Abstract
The invention relates to a method for increasing yields of ethylene and propylene. 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 refinery C4 fraction, namely a mixture of C4 alkane and olefin generated from a refinery, as a raw material; and the refinery C4 fraction is converted into a cracking product rich in the propylene and the ethylene through a catalytic cracking reaction and an alkane catalytic dehydrogenation reaction, and the cracking product is fed back the separation system of a catalytic cracker to finish the separation and purification of the cracking product. The C4 alkane part of the raw material is converted into C4 olefin through catalytic dehydrogenation process and is fed back to join the catalytic cracking reaction such that the C4 alkane of the raw material is fully utilized. The invention is characterized in that: a few catalytic cracking and alkane catalytic dehydrogenation reactors and a simple separating device are additionally provided, thus the C4 raw material of the refinery can be effectively converted into the cracking product rich in the propylene and the ethylene, the potential of the separation system of a current steam cracking device can be fully tapped, and the yields of the ethylene and the propylene are increased; simultaneously, the advantages of the catalytic cracking reaction and the alkane catalytic dehydrogenation are combined, thus the utilization value of the refinery C4 can be effectively increased, and the full utilization of the refinery C4 raw material can be also realized. The method disclosed by the invention can be applied to the current steam cracking devices, thus the utilization efficiency of the raw material is increased, and the economic benefit of corporation is increased.
Description
Technical field
The present invention relates to a kind of method of propylene enhancing, ethene, more particularly, the present invention relates to a kind of method utilizing existing preparing ethylene by steam cracking device and separation system thereof to improve propylene and ethylene yield.
Background technology
Ethene and propylene are important basic chemical raw materials.In Industrial processes, ethene and propylene are mainly through steam cracking (i.e. thermo-cracking) explained hereafter.In steam cracking production equipment, after the cracking stocks such as lighter hydrocarbons, petroleum naphtha, hydrogenation tail oil, solar oil mix with water vapour, in pyrolyzer, there is heat scission reaction, generate the 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 carbonatoms, then isolate ethene and propylene product from carbon two, C3 fraction.
In recent years, along with the quick growth of domestic economy, the market requirement of the low-carbon alkene such as ethene, propylene is increasing, and the original throughput of domestic ethene, propylene can not meet the market requirement increased rapidly, therefore China's ethene, propylene of all wanting import a large amount of every year.For alleviating the disparities between supply and demand of state's inner propene, Market for Ethylene, fill up demand gap, China starts the reconstruction and extension project that second and third takes turns ethylene industry in recent years continuously, and before 2010, China is by the olefin plant of appearance tens scales 80 ~ 1,200,000 tons of ethene/years.In a foreseeable future, the imbalance between supply and demand in the low-carbon alkene market such as state's inner propene, ethene will be eased.It should be noted that, the cracking stock that these scales use in the olefin plant in 80 ~ 1,200,000 tons of ethene/years all belongs to traditional steam crack material, such as petroleum naphtha, hydrogenation tail oil, lighter hydrocarbons etc., and crude capacity supporting with it does not obtain corresponding raising, traditional cracking stock shortage or cracking stock quality may be caused to decline, thus make the separation in steam cracking process (recovery) system may there is larger operation surplus in actual production.Therefore, how to expand raw material sources to improve propylene in steam cracking process, ethylene yield becomes the important factor affecting Business Economic Benefit.
Refinery casing head is mainly from catalytic cracking unit (FCC), although the also by-product C-4-fraction such as viscosity breaking, thermally splitting and coking, and 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, and the feature of its fractions consisting is butylene massfraction is about 50%, and hardly containing divinyl, rest part is butane.The utilization of China's refinery's C-4-fraction generally divides two kinds, i.e. direct industrial utilization and be separated chemical utilization afterwards.Direct industrial utilization comprises: directly send into liquefied petroleum gas (LPG) without processing and use as fuel; Mix gasoline to regulate its vapour pressure, be directly used as fuel gas; And generate the liquid fuel such as gasoline alkylate, MTBE (methyl tertiary butyl ether) through chemical process.Wherein, the higher Land use systems of added value is gasoline alkylate and MTBE, but due to its grievous injury manufacturing and cause for environment in use procedure, this kind of utilization ways has not been the developing direction of Future Refineries carbon four utilization of resources technology.After being separated, chemical utilization is carried out by refinery's C-4-fraction being separated, refining, and is then used as the raw material producing various Chemicals.Because the boiling point of cut each in refinery's C-4-fraction is very close, relative volatility and the zero pour difference of some cut are minimum, simple distillation method is adopted to be difficult to effective separation, the energy expenditure that low temperature crystallization is separated is also very considerable, and these two kinds of separation methods are all difficult to the purity ensureing separate fraction, therefore also will carry out follow-up refinement treatment, tooling cost is higher.As can be seen here, for the C-4-fraction that refinery produces, how could in addition environmental protection and the utilization of high added value, become the problem that current refinery is in the urgent need to address.
C 4 olefin can be converted into propylene and ethene by catalytic pyrolysis process effectively, temperature of reaction can far below existing steam-cracking process, and catalytic pyrolysis product composition is similar to steam cracking product, but owing to being subject to the restriction of thermodynamic(al)equilibrium, C 4 olefin is difficult to realize transforming completely.The speed of reaction of butane in above-mentioned catalytic cracking reaction far below C 4 olefin, especially at a lower temperature, butane sluggish.Therefore, if cracking c_4 alkane and olefin logistics are sent into catalytic cracking reaction device, then most of butane will enter in the catalytically cracked gas of reaction generation.Therefore, in order to process alkane cracking better, after Deep Catalytic Cracking process, add alkane catalytic dehydrogenation process.
In alkane catalytic dehydrogenation processes, alkane catalytic dehydrogenation processes not only can make separating obtained paraffin section raw material be realized to conversion of olefines by dehydrogenation, and can by obtain the raw material being rich in C 4 olefin and enter catalytic cracking system by circulation, again effectively be converted into propylene and ethene in the mode of olefins by catalytic cracking, both solved the conversion of alkane to low-carbon alkene ethene and propylene, the olefins by catalytic cracking unit of upstream flow process can have been made full use of again.
Summary of the invention
The present invention is in order to alleviate the imbalance between supply and demand in the low-carbon alkene markets such as domestic ethene, propylene, the utilising efficiency that in abundant excavation steam cracking process, cracking is separated, make full use of butane and olefin material improve its value of the product that refinery produces, propose and increase catalytic cracking system to improve the method for propylene and ethylene yield in existing steam cracking process.
The butane that method provided by the invention produces with refinery and olefin material are for raw material, catalytic pyrolysis process and alkane catalytic dehydrogenation processes are combined, olefins by catalytic cracking and mixed alkene and alkane catalytic cracking reaction is utilized to make most of C 4 olefin and part butane in butane and alkene mixture be cracked into propylene in catalytic cracking system, ethene and other byproducts, recycling alkane catalytic dehydrogenation processes makes the butane catalytic dehydrogenation of failing in catalytic pyrolysis process to transform be converted into the material being rich in C 4 olefin, and this Matter Transfer is entered catalyst cracking unit, catalytic dehydrogenation gained C 4 olefin is further converted to and is rich in ethene by the olefins by catalytic cracking function be fully beneficial in catalyst cracking unit, propylene split product, the alkane in described catalytically cracked gas is made to be alkene by dehydrogenation and can fully to transform, improve the yield of ethene and propylene.Logistics after catalytic cracking system generation also simple separation is sent into the separation system of steam cracking device by the present invention again, fully can excavate the production potential of existing separation system.Utilize alkane catalytic dehydrogenation processes that separating obtained paraffin section raw material not only can be made to be realized to conversion of olefines by dehydrogenation, and can by obtain the raw material being rich in C 4 olefin and enter catalytic cracking system by circulation, again effectively be converted into propylene and ethene in the mode of olefins by catalytic cracking, both the conversion of alkane to low-carbon alkene ethene and propylene had been solved, the olefins by catalytic cracking unit of upstream flow process can be made full use of again, achieve making full use of of refinery C four.The catalytic cracking system that can be so just raw material with the butane of refinery's generation and alkene mixture by increase, improves propylene and the ethylene yield of steam cracking device.
Concrete technical scheme is as follows:
The method of propylene enhancing of the present invention and ethylene yield, catalytic cracking system is set up in steam cracking and tripping device, described catalytic cracking system comprises C _ 4 alkene catalytic pyrolysis unit, mixed alkene and alkane catalyst cracking unit, butane catalytic dehydrogenation unit and separating unit, the method, comprises the following steps for raw material with refinery's C-4-fraction:
(1) C _ 4 alkene catalytic pyrolysis: send into C _ 4 alkene catalytic pyrolysis unit by described from refinery's C-4-fraction, described butane and alkene mixture are converted into the catalytically cracked gas being rich in ethene and propylene at least in part;
(2) alkane alkene mixture catalytic pyrolysis: isolate carbon more than four cut from the catalytically cracked gas that step (1) obtains, sent into mixed alkene and alkane catalytic cracking system, described carbon more than four cut is converted into the catalytically cracked gas being rich in propylene and ethene at least in part;
(3) alkane catalytic dehydrogenation: isolate the logistics containing butane from the catalytically cracked gas that step (2) obtains, and sent into butane catalytic dehydrogenation unit, make described at least part of being converted into of logistics containing butane be rich in the dehydrogenation logistics of C 4 olefin, and the C _ 4 alkene catalytic pyrolysis unit described in step (1) is introduced in this logistics circulation.
(4) product reclaims: isolate carbon less than three cut in the catalytically cracked gas obtained from step (1) and step (2), sent in the splitting gas of the oil scrubber of steam cracking and tripping device, water wash column or compressor, with the output of the propylene and ethene that improve steam cracking device.
Preferably, in described C _ 4 alkene catalytic pyrolysis unit, described butane and olefin mixture feed are converted into the catalytically cracked gas logistics 1 being rich in propylene and ethene at least in part, the logistics 2 of carbon less than three cut and the logistics 3 of carbon more than four cut is separated into after cooling, described carbon more than four cut 3 is sent into described mixed alkene and alkane catalyst cracking unit, described carbon more than four cut 3 is converted into the logistics 4 being rich in propylene and ethene at least in part, the logistics 5 containing C-4-fraction is separated into after cooling, the logistics 6 of carbon less than three cut and the logistics 7 of carbon more than five, logistics 5 is sent into described butane catalytic dehydrogenation unit, in described butane catalytic dehydrogenation unit, described C-4-fraction is converted into catalytic dehydrogenation gas logistics 8, logistics 8 is circulated and introduces C _ 4 alkene catalytic pyrolysis unit, logistics 6 is sent into together with logistics 2 oil scrubber of steam cracking and tripping device, in the splitting gas of water wash column or compressor, with the output of the propylene and ethene that improve steam cracking device.
Preferably, after described catalytically cracked gas logistics 1 cools, first be separated into the logistics of carbon less than five cut and the logistics of carbon more than six cut, then the logistics of carbon less than five cut is separated into the logistics 2 of carbon less than three cut and the logistics of carbon four carbon five mixed fraction, then the butane catalytic dehydrogenation unit described in sending into after the logistics of carbon more than six cut is mixed with the logistics of carbon four carbon five mixed fraction; Described catalytically cracked gas logistics 4 cools rear separation and obtains the logistics of carbon more than six cut and the logistics of carbon less than five cut, from the logistics of carbon less than five cut, then isolate the logistics 6 of carbon less than three cut.
Preferably, the logistics of isolated carbon more than five cut from the product that described catalytic cracking system generates, by its recycle or deliver to pyrolysis gasoline hydrogenation device.
Preferably, it is 0 ~ 100 DEG C that described catalytically cracked gas and catalytic dehydrogenation product carry out cooling with the temperature range be separated, preferably 0 ~ 40 DEG C.
Preferably, the catalyzer of described C _ 4 alkene catalytic pyrolysis unit and mixed olefins and the use of alkane catalyst cracking unit is modification or unmodified SAPO-34, ZSM-5, ZSM-11, ZSM-23, MCM-22, MCM-49, one or more of MCM-56 and mordenite, modifying element comprises phosphorus, lanthanum, cerium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, cadmium, zirconium, molybdenum, one or more in tungsten and aluminium, during modification, metal-salt used is the carbonate of above-mentioned selected metal, vitriol, nitrate, oxalate, phosphoric acid salt, muriate or ammonium salt.
Preferably, the catalyzer that described carbon four catalytic dehydrogenation unit uses is the catalyzer at the supported on carriers activeconstituents with regular or non-regular pore passage structure, activeconstituents wherein can be one or more in platinum, chromium, tin, palladium, lead, aluminium, vanadium, titanium, zirconium, cerium, molybdenum, niobium, zinc, magnesium and nickel, also can be a kind of oxide compound of above-mentioned metal or the hopcalite of multiple above-mentioned metal or sosoloid.
Preferably, the temperature of reaction of described C _ 4 alkene catalytic pyrolysis unit is 400 ~ 600 DEG C, and reaction pressure is 0.07 ~ 0.50MPa, and during liquid, volume space velocity is 0.5 ~ 100h
-1, the charge-mass ratio of water vapour and catalytic pyrolysis raw material is 0 ~ 10; The temperature of reaction of described mixed olefins and alkane catalyst cracking unit is 450 ~ 650 DEG C, and reaction pressure is 0.07 ~ 0.50MPa, and during liquid, volume space velocity is 0.5 ~ 100h
-1, the charge-mass ratio of water vapour and catalytic pyrolysis raw material is 0 ~ 10.
Preferably, the temperature of reaction of described butane catalytic dehydrogenation unit is 520 ~ 680 DEG C, and reaction pressure is 0.01 ~ 0.07MPa, and reactant flow volume air speed is 1 ~ 10h
-1.
Preferably, described refinery C-4-fraction introduction volume needs the ability to bear according to steam heat cracking steam cracking separation system and determines.
The present invention is outside existing steam cracking and tripping device system, increase the catalytic cracking system that a butane produced with refinery's C-4-fraction and refinery and alkene mixture are raw material, catalytic cracking reaction process and alkane catalytic dehydrogenating reaction process is utilized to combine, butane and alkene mixture is made to change the split product of propylene, ethene and other by-products into, and these split products are after simple refrigerated separation, the separation system being admitted to steam cracking process carries out separating-purifying.
Catalytic cracking system comprises C _ 4 alkene catalytic pyrolysis unit, mixed alkene and alkane catalyst cracking unit, butane catalytic dehydrogenation unit and separating unit.The raw material of C _ 4 alkene catalytic pyrolysis unit is butane from refinery's C-4-fraction and alkene mixture, and this raw material is converted into the catalytically cracked gas being rich in propylene and ethene in C _ 4 alkene catalytic pyrolysis unit.C _ 4 alkene catalytic pyrolysis unit, mixed alkene and alkane catalyst cracking unit can adopt one or more combination in fixed-bed reactor, moving-burden bed reactor, fluidized-bed reactor.The catalytically cracked gas that C _ 4 alkene catalytic pyrolysis unit produces is cooled and is separated and obtains carbon less than three cut and carbon more than four cut, above-mentioned carbon less than three cut is sent into the appropriate location of steam cracking device separation system, and carbon more than four cut is sent into alkane catalytic dehydrogenation system.
C _ 4 alkene 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 comprise in phosphorus, lanthanum, cerium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, cadmium, zirconium, molybdenum, tungsten or aluminium one or more, during modification, metal-salt used is the carbonate of above-mentioned selected metal, vitriol, nitrate, oxalate, phosphoric acid salt or muriate, also can be corresponding ammonium salt etc.Alkene component in butane and alkene mixture can be converted into the catalytically cracked gas being rich in propylene and ethene by this catalyzer at least in part.The temperature of reaction of C _ 4 alkene catalytic pyrolysis unit is 400 ~ 600 DEG C, and reaction pressure is 0.07 ~ 0.50MPa, and during liquid, volume space velocity is 0.5 ~ 100h
-1, the charge-mass ratio of water vapour and butane and alkene mixture is 0 ~ 10.
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 comprise in phosphorus, lanthanum, cerium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, cadmium, zirconium, molybdenum, tungsten or aluminium one or more, during modification, metal-salt used is the carbonate of above-mentioned selected metal, vitriol, nitrate, oxalate, phosphoric acid salt or muriate, also can be corresponding ammonium salt etc.Carbon four to carbon nine alkene in catalytic pyrolysis raw material and paraffins mixture can be converted into the catalytically cracked gas being rich in propylene and ethene by mixed olefins and alkane catalytic cracking catalyst in whole or in part.Mixed olefins and alkane catalytic cracking catalyst range of reaction temperature are 500 ~ 750 DEG C, and reaction pressure (gauge pressure) scope is 0.07 ~ 0.50MPa, and water and weight of material ratio are 0 ~ 10, and material feeding space velocity range is 0.5 ~ 100h
-1.
The raw material of butane catalytic dehydrogenation unit is listened in the catalytically cracked gas produced with alkane catalyst cracking unit by mixing alkene to be separated the butane cut obtained.Above-mentioned raw materials is converted into the catalytically cracked gas being rich in C 4 olefin in butane catalytic dehydrogenation unit.Butane catalytic dehydrogenation unit uses catalyzer, and alkane catalytic dehydrogenation unit adopts one or more combination in tubular reactor, fixed-bed reactor, moving-burden bed reactor, fluidized-bed reactor.The logistics that butane catalytic dehydrogenation unit produces is recycled and enters catalyst cracking unit and transform further to generate and be rich in the catalytically cracked gas of propylene and ethene.
The catalyzer that carbon four catalytic dehydrogenation unit uses can be the catalyzer at the upper carrying active ingredients of the carrier with regular or non-regular pore passage structure (as aluminum oxide, silicon oxide, porous zeolite, spherical silica gel, kaolin, ZSM-5 or SAPO-34 molecular sieve), activeconstituents wherein can be one or more in the metals such as platinum, chromium, tin, palladium, lead, aluminium, vanadium, titanium, zirconium, cerium, molybdenum, niobium, zinc, magnesium, nickel, also can be a kind of oxide compound of above-mentioned metal or the hopcalite of multiple above-mentioned metal or sosoloid.The feedstock conversion that the mixture of butane and alkene can form by this catalyzer is the logistics being rich in C 4 olefin, and the C 4 olefin material obtained follows and enters olefins by catalytic cracking reaction member, to improve the transformation efficiency of C-4-fraction.Butane catalytic dehydrogenating reaction temperature is 520 ~ 680 DEG C, and reaction pressure is 0.01 ~ 0.07MPa, and during liquid, volume space velocity is 1 ~ 10h
-1.
Catalyzer mentioned in the present invention all can adopt existing catalyst preparation technology to prepare, and Beijing Chemical Research Institute can produce described catalyzer.
In sum, to add the butane that produces with refinery and alkene mixture in existing steam cracking process be raw material catalytic cracking system, butane and olefin mixture feed is made to be partially converted into propylene and ethene, simultaneously by butane catalytic dehydrogenation being converted into the dehydrogenation logistics being rich in C 4 olefin, and circulation introducing C _ 4 alkene catalytic pyrolysis unit is further converted to the split product being rich in ethene and propylene, effectively improves the low-carbon alkene transformation efficiency of C 4 materials.The product material produced by this catalytic cracking system carries out initial gross separation, and the appropriate location of the separation system in steam cracking process is sent in each logistics separation obtained, both the production potential of the separation system of steam cracking process had effectively been excavated, more improve utilising efficiency and the value promotion of refinery C four raw material, improve the propylene of steam cracking flow process, the output of ethene simultaneously, add the economic benefit of enterprise.
Embodiment
The present invention is further described below in conjunction with embodiment.Scope of the present invention does not limit by these embodiments.
Comparative example 1
The olefin plant of certain 1,000,000 tons/year of ethene, has 11 pyrolyzer, and wherein 6 is light oil cracking stove, 3 heavy oit pyrolysis stoves, and 1 is light hydrocarbon cracking stove, and 1 is pyrolyzer for subsequent use.Light oil cracking stove is based on naphtha cracking, and heavy oit pyrolysis stove is cracked into master with hydrogenation tail oil, and light hydrocarbon cracking stove is based on cycle ethane and Deposition During Propane Pyrolysis.Each pyrolyzer charging capacity is in table 1, and ethene, propylene, butane butylene yield and output are in table 2.
1,000,000 tons of olefin plant cracking stock years of table 1 throw 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 product yields and output
| Ultimate production, ten thousand tons/year | Total recovery, wt% | |
| Ethene | 100.262 | 30.97 |
| Propylene | 50.722 | 15.67 |
From table 1 and table 2, these cracking stocks generate mixed pyrolysis gas through pyrolyzer thermo-cracking, and mixed pyrolysis gas, after separation system separating-purifying, can be produced every year:
(1) the complete total annual production of factory's ethene is 100.64 ten thousand tons, and full factory ethene total recovery is 30.97%;
(2) the complete total annual production of factory's propylene is 47.56 ten thousand tons, and full factory propylene total recovery is 15.67%.
Embodiment 1
Adopt method of the present invention, on the basis of comparative example 1, increase catalytic cracking system, the butane produced with oil refining process and alkene mixture (composition is as shown in table 3), for raw material, increase production propylene and the ethene of steam cracking device.The treatment capacity of refinery C four raw material is 100,000 tons/year.Catalytic cracking system comprises C _ 4 alkene catalytic pyrolysis unit, mixed olefins and alkane catalyst cracking unit, butane catalytic dehydrogenation unit and separating unit.
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 |
Concrete grammar is as follows:
(1) C _ 4 alkene catalytic pyrolysis unit is sent into together with the logistics that the C 4 olefin and the paraffins mixture raw material that are first produced refinery and follow-up workshop section loop back, there is catalytic cracking reaction in the C 4 olefin in raw material, temperature of reaction is 550 DEG C, reaction pressure (gauge pressure) is 0.15MPa, air speed is 3h under the effect of catalyzer
-1.The C 4 olefin generation catalytic cracking reaction of 70%, generate the low-carbon alkene such as propylene, ethene and carbon more than five hydro carbons by product, converting feedstock is the logistics 1 being rich in propylene, ethene, and wherein propylene content is 18.3wt%, and ethylene content is 5.7wt%.The catalyzer that C _ 4 alkene catalytic pyrolysis unit adopts is the ZSM-5 molecular sieve type catalyzer of modification, it consists of: (silica alumina ratio is 100 for phosphorus 5wt%, lanthanum 2wt%, ZSM-5 molecular sieve 64wt%, particle diameter is 500nm), silicon oxide 29wt%, produced by Beijing Chemical Research Institute.
(2) logistics 1 is cooled also rectifying separation, obtain logistics 2 and logistics 3, wherein logistics 2 is carbon less than five cut, and logistics 3 is carbon more than six cut containing a small amount of carbon five.
(3) logistics 2 is compressed to rectifying separation after suitable pressure, obtain logistics 4 and logistics 5, logistics 4 is carbon less than three cut, and logistics 5 is carbon four carbon five mixed fraction.
(4) logistics 3 is mixed with logistics 5, obtain logistics 6.
(5) logistics 6 is passed into mixed alkene and alkane catalyst cracking unit, make logistics 3, under catalyst action, catalytic cracking reaction occur, temperature of reaction is 600 DEG C, and reaction pressure (gauge pressure) is 0.15MPa, and during liquid, volume space velocity is 3h
-1.Most of carbon in logistics 3 four is to carbon eight alkene generation catalytic cracking reaction, and logistics 3 is changed be rich in into the logistics 4 of propylene and ethene, the propylene content wherein in logistics 4 is 12.6wt%, and ethylene content is 4.0wt%.This mixed alkene and alkane catalyst cracking unit catalyzer used consist of: (silica alumina ratio is 140 for phosphorus 4wt%, lanthanum 3wt%, calcium 2wt%, silver-colored 2wt%, ZSM-5 molecular sieve 60wt%, particle diameter is 400nm), silicon oxide 29wt%, produced by Beijing Chemical Research Institute.
(6) logistics 4 cooled, be separated, obtain logistics 7, logistics 8 and logistics 9, wherein logistics 7 is carbon less than three cut, and logistics 8 is the C-4-fraction containing a small amount of carbon five, and logistics 9 is carbon more than five cut.
(7) butane catalytic dehydrogenation unit is sent in logistics 8.Alkane catalyst cracking unit catalyst filling, its temperature of reaction is 600 DEG C, reaction pressure (gauge pressure) is 0.05MPa, liquid time volume space velocity be 3h
-1.There is alkane catalytic dehydrogenating reaction in logistics 8, generate the logistics 10 being rich in C 4 olefin, the flow of logistics 10 is 7.33 ten thousand tons/year, and wherein C 4 olefin content is 60%.
(8) logistics 10 is sent back to the inlet duct of C _ 4 alkene catalytic pyrolysis unit.
(9) logistics 4 and logistics 7 are mixed, obtain logistics 11.
(10) controlling the temperature of logistics 11 is within the scope of 230 ~ 250 DEG C, and controls its pressure and be greater than 0.7MPa, logistics 11 is passed in the splitting gas pipeline in the separation system of steam cracking process in oil scrubber.
(11) logistics 9 is sent into the pyrolysis gasoline hydrogenation device of steam cracking process.
Can be calculated by the state of arts in the present embodiment, after to the addition of the C 4 olefin that produces with refinery and paraffins mixture in existing steam cracking device be raw material catalytic cracking system, relative to comparative example 1, the propylene annual production of steam cracking device improves 4.72 ten thousand tons, ethene annual production improves 1.47 ten thousand tons, the propene yield of refinery C four reaches 47.2%, and yield of ethene reaches 14.7%.
As can be seen here, in original steam cracking process process, increase the catalytic cracking system being raw material with the C 4 olefin produced in oil refining process and paraffins mixture, when increasing a small amount of catalytic cracking reaction device, full factory ethene and productivity of propylene are significantly improved, and are conducive to enterprise and increase economic efficiency.
Claims (5)
1. the method for a propylene enhancing and ethylene yield, it is characterized in that, catalytic cracking system is set up in steam cracking and tripping device, described catalytic cracking system comprises C _ 4 alkene catalytic pyrolysis unit, mixed alkene and alkane catalyst cracking unit, butane catalytic dehydrogenation unit and separating unit, the method, comprises the following steps for raw material with refinery's C-4-fraction:
(1) C _ 4 alkene catalytic pyrolysis: send into C _ 4 alkene catalytic pyrolysis unit by described from refinery's C-4-fraction, described butane and alkene mixture are converted into the catalytically cracked gas being rich in ethene and propylene at least in part;
(2) alkane alkene mixture catalytic pyrolysis: isolate carbon more than four cut from the catalytically cracked gas that step (1) obtains, sent into mixed alkene and alkane catalytic cracking system, described carbon more than four cut is converted into the catalytically cracked gas being rich in propylene and ethene at least in part;
(3) alkane catalytic dehydrogenation: isolate the logistics containing butane from the catalytically cracked gas that step (2) obtains, and sent into butane catalytic dehydrogenation unit, make described at least part of being converted into of logistics containing butane be rich in the dehydrogenation logistics of C 4 olefin, and the C _ 4 alkene catalytic pyrolysis unit described in step (1) is introduced in this logistics circulation;
(4) product reclaims: isolate carbon less than three cut in the catalytically cracked gas obtained from step (1) and step (2), sent in the splitting gas of the oil scrubber of steam cracking and tripping device, water wash column or compressor, with the output of the propylene and ethene that improve steam cracking device;
The catalyzer that described C _ 4 alkene catalytic pyrolysis unit and mixed olefins and alkane catalyst cracking 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 is one or more in phosphorus, lanthanum, cerium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, cadmium, zirconium, molybdenum, tungsten and aluminium, and during modification, metal-salt used is the carbonate of above-mentioned selected metal, vitriol, nitrate, oxalate, phosphoric acid salt, muriate or ammonium salt;
The catalyzer that described carbon four catalytic dehydrogenation unit uses is the catalyzer at the supported on carriers activeconstituents with regular or non-regular pore passage structure, activeconstituents is wherein one or more in platinum, chromium, tin, palladium, lead, aluminium, vanadium, titanium, zirconium, cerium, molybdenum, niobium, zinc, magnesium and nickel, or the hopcalite of a kind of oxide compound of above-mentioned metal or multiple above-mentioned metal or sosoloid;
The temperature of reaction of described C _ 4 alkene catalytic pyrolysis unit is 400 ~ 600 DEG C, and reaction pressure is 0.07 ~ 0.50MPa, and during reaction solution, volume space velocity is 0.5 ~ 100h
-1, the charge-mass ratio of water vapour and catalytic pyrolysis raw material is 0 ~ 10; The temperature of reaction of described mixed olefins and alkane catalyst cracking unit is 450 ~ 650 DEG C, and reaction pressure is 0.07 ~ 0.50MPa, and during reaction solution, volume space velocity is 0.5 ~ 100h
-1, the charge-mass ratio of water vapour and catalytic pyrolysis raw material is 0 ~ 10; The temperature of reaction of described butane catalytic dehydrogenation unit is 520 ~ 680 DEG C, and reaction pressure is 0.01 ~ 0.07MPa, and reactant flow volume air speed is 1 ~ 10h
-1.
2. the method for propylene enhancing as claimed in claim 1 and ethylene yield, it is characterized in that, in described C _ 4 alkene catalytic pyrolysis unit, described butane and olefin mixture feed are converted into the catalytically cracked gas logistics 1 being rich in propylene and ethene at least in part, the logistics 2 of carbon less than three cut and the logistics 3 of carbon more than four cut is separated into after cooling, described carbon more than four cut 3 is sent into described mixed alkene and alkane catalyst cracking unit, described carbon more than four cut 3 is converted into the logistics 4 being rich in propylene and ethene at least in part, the logistics 5 containing C-4-fraction is separated into after cooling, the logistics 6 of carbon less than three cut and the logistics 7 of carbon more than five, logistics 5 is sent into described butane catalytic dehydrogenation unit, in described butane catalytic dehydrogenation unit, described C-4-fraction is converted into catalytic dehydrogenation gas logistics 8, logistics 8 is circulated and introduces C _ 4 alkene catalytic pyrolysis unit, logistics 6 is sent into together with logistics 2 oil scrubber of steam cracking and tripping device, in the splitting gas of water wash column or compressor, with the output of the propylene and ethene that improve steam cracking device.
3. the method for propylene enhancing as claimed in claim 2 and ethylene yield, it is characterized in that, after described catalytically cracked gas logistics 1 cools, first be separated into the logistics of carbon less than five cut and the logistics of carbon more than six cut, then the logistics of carbon less than five cut is separated into the logistics 2 of carbon less than three cut and the logistics of carbon four carbon five mixed fraction, then the butane catalytic dehydrogenation unit described in sending into after the logistics of carbon more than six cut is mixed with the logistics of carbon four carbon five mixed fraction; Described catalytically cracked gas logistics 4 cools rear separation and obtains the logistics of carbon more than six cut and the logistics of carbon less than five cut, then the logistics of carbon less than five cut is isolated the logistics 6 of carbon less than three cut.
4. the method for increasing output of ethylene as claimed in claim 2 and propone output, is characterized in that, the logistics of isolated carbon more than five cut from the product that described catalytic cracking system generates, by its recycle or deliver to pyrolysis gasoline hydrogenation device.
5. the method for increasing output of ethylene as claimed in claim 2 and propone output, it is characterized in that, it is 0 ~ 100 DEG C that described catalytically cracked gas carries out cooling with the temperature range be separated.
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| CN104557396B (en) * | 2013-10-23 | 2017-10-27 | 中国石油化工股份有限公司 | A kind of method of n-butene catalytic cracking for producing propylene |
| CN104557397B (en) * | 2013-10-23 | 2017-03-22 | 中国石油化工股份有限公司 | Method for producing propylene from n-butene |
| CN114456025B (en) * | 2020-10-21 | 2024-05-28 | 中国石油化工股份有限公司 | Method and system for producing ethylene and propylene by catalyzing light gasoline |
| CN116554923B (en) * | 2022-01-28 | 2024-10-11 | 中国石油化工股份有限公司 | Method and system for producing low-carbon olefin by heavy oil |
| CN115888797B (en) * | 2022-11-08 | 2024-08-06 | 洛阳市科创石化科技开发有限公司 | Catalyst for preparing ethylene and propylene by cracking carbon five-carbon hexaalkane and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101205162A (en) * | 2006-12-21 | 2008-06-25 | 中国石油化工股份有限公司 | Combined technique for preparing olefins by using refinery C4 |
| CN101255086A (en) * | 2007-03-01 | 2008-09-03 | 中国石油化工股份有限公司 | Method for Cracking C_4 and preparing olefin by refinery C_4 |
| CN101734987A (en) * | 2008-11-07 | 2010-06-16 | 中国石油化工股份有限公司 | Method for preparing ethylene and propylene from C4 hydrocarbons |
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| CN101165026B (en) * | 2006-10-20 | 2011-01-19 | 中国石油化工股份有限公司上海石油化工研究院 | Method for producing ethylene and propylene from methanol and dimethyl ether |
| CN101165017B (en) * | 2006-10-20 | 2010-08-18 | 中国石油化工股份有限公司 | Production increasing method for propylene |
| CN101239878B (en) * | 2007-02-07 | 2010-05-19 | 中国石油化工股份有限公司 | Method for increasing yield of ethylene and propylene from olefin with four carbon or above |
| CN101147874B (en) * | 2007-11-06 | 2011-04-20 | 东南大学 | Catalyst for preparing propylene and ethylene by C4 olefins and preparation method |
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| CN101255086A (en) * | 2007-03-01 | 2008-09-03 | 中国石油化工股份有限公司 | Method for Cracking C_4 and preparing olefin by refinery C_4 |
| CN101734987A (en) * | 2008-11-07 | 2010-06-16 | 中国石油化工股份有限公司 | Method for preparing ethylene and propylene from C4 hydrocarbons |
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