CN104250190B - A kind of preparation method of propylene - Google Patents
A kind of preparation method of propylene Download PDFInfo
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- CN104250190B CN104250190B CN201310269035.0A CN201310269035A CN104250190B CN 104250190 B CN104250190 B CN 104250190B CN 201310269035 A CN201310269035 A CN 201310269035A CN 104250190 B CN104250190 B CN 104250190B
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Abstract
The invention provides a kind of preparation method of propylene, the method comprises: (1) isolates below C3 component from liquefied petroleum gas (LPG), 1-butylene content be more than 20 % by weight be rich in 1-butylene component, 2-butylene content be more than 20 % by weight be rich in 2-butylene component; (2) under the existence of alkene exchange catalysts, be rich in 2-butylene component and ethene carries out alkene permutoid reaction by described, make at least part of 2-butylene be converted to propylene, and exchange product from alkene and isolate propylene and butane; And/or under the existence of catalyst for cracking, the described 1-butylene component that is rich in is carried out catalytic cracking reaction, makes at least part of 1-butylene be converted into propylene, and from catalytic cracking reaction products, isolate propylene and butane; (3) by described below C3 component with to exchange product isolated butane from alkene and/or isolated butane carries out steam cracking reaction from catalytic cracking reaction products.Adopt the method can obtain higher propene yield.
Description
Technical field
The present invention relates to a kind of preparation method of propylene.
Background technology
Propylene (propylene, CH
2=CHCH
3) at normal temperatures for colourless, odorless, slightly with pleasantly sweet gas.Propylene is the important Organic Chemicals being only second to ethene, in order to produce multiple important Organic Chemicals, to generate synthetic resins, synthetic rubber and multiple fine chemicals etc., mainly comprise polypropylene, vinyl cyanide, vinylformic acid, isopropyl alkene, acetone, propylene oxide etc., be widely used in national economy every field.The mode of production of propylene mainly contains three kinds: steam cracking process (being the joint product of ethylene production), refinery catalytic cracking technique and dehydrogenating propane technique.Wherein, propylene is mainly derived from steam cracking process, and its output reaches more than 65% of propylene ultimate production, be secondly refinery catalytic cracking technique, and the industrial application of dehydrogenating propane technique is less.In recent years, due to the fast development of propylene derived product, greatly facilitate the quick growth of Chinese propylene demand.Estimate 2015, China's propylene production capacity reaches 2,400 ten thousand tons, and output reaches 2,160 ten thousand tons, and the demand gap dependence on import of about 6,400,000 tons solves.Therefore, China's propylene exploitation prospect is wide.
Main containing C4 component in described liquefied petroleum gas (LPG) (being called for short LPG), also may contain a small amount of below C3 component and/or more than C5 component.Wherein, below C3 component is mainly containing propane.C4 component, also may containing a small amount of iso-butylene and 1,3-micro-dibutene mainly containing Trimethylmethane, normal butane, n-butene.The component of more than C5 is mainly containing pentane, Benzene and Toluene.In the liquefied petroleum gas (LPG) of different sources, the content of said components may also exist larger difference.
Along with the maximization of petroleum chemical enterprise's production equipment scale, the processing power of China's single cover oil refining apparatus is more than 1,000 ten thousand tons/year, and the ethylene production capacity of ethylene unit supporting with it also reaches 80-120 ten thousand tons/year.The output of the liquefied petroleum gas (LPG) that oil refining and ethylene unit are produced improves year by year.At present, the annual production of China's liquefied petroleum gas (LPG) is more than 1,000 ten thousand tons.The liquefied petroleum gas (LPG) of petrochemical enterprise in China by-product is mainly used in the production of civil LPG, only have and produce gasoline and aromatic hydrocarbons for alkylation and aromizing on a small quantity, comprehensive utilization ratio is lower than 15%, well below the U.S., Japan and West Europe more than 50% utilize level, cause the economic value added of liquefied petroleum gas (LPG) resource low.And constantly increase along with the Sweet natural gas consumption of clean domestic fuel, the dim future that liquefied petroleum gas (LPG) uses as fuel.Therefore, make full use of liquefied petroleum gas (LPG) resource, improve its comprehensive utilization ratio and economic value added and become one of important channel of the economic benefit improving Petrochemical Enterprises.
Summary of the invention
The object of the invention is the defect that liquefied petroleum gas (LPG) utilization ratio and Economic Value Added in order to overcome prior art is low, and a kind of method adopting liquefied petroleum gas (LPG) to prepare propylene is provided, adopt the method can obtain higher propene yield.
The invention provides a kind of preparation method of propylene, the method comprises the following steps:
(1) from liquefied petroleum gas (LPG), isolate below C3 component, 1-butylene content be more than 20 % by weight be rich in 1-butylene component, 2-butylene content be more than 20 % by weight be rich in 2-butylene component;
(2) under the existence of alkene exchange catalysts, be rich in 2-butylene component and ethene carries out alkene permutoid reaction by described, make at least part of 2-butylene be converted to propylene, and exchange product from alkene and isolate propylene and butane; And/or
Under the existence of catalyst for cracking, the described 1-butylene component that is rich in is carried out catalytic cracking reaction, makes at least part of 1-butylene be converted into propylene, and from catalytic cracking reaction products, isolate propylene and butane;
(3) will from step (1) isolated described below C3 component with to exchange product isolated butane from alkene and/or isolated butane carries out steam cracking reaction from catalytic cracking reaction products.
The propylene adopting method provided by the invention to prepare is made up of three parts, from alkene exchange product be separated obtain propylene, from catalytic cracking reaction products, be separated the propylene that obtains and from steam cracking reaction product, be separated the propylene obtained.As can be seen from the result of embodiment, the yield being only separated the propylene obtained from steam cracking reaction product just can reach more than 30.34%, that is, adopt the method for the application can obtain higher propene yield, thus improve utilization ratio and the Economic Value Added of liquefied petroleum gas (LPG).
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The preparation method of propylene provided by the invention comprises the following steps:
(1) from liquefied petroleum gas (LPG), isolate below C3 component, 1-butylene content be more than 20 % by weight be rich in 1-butylene component, 2-butylene content be more than 20 % by weight be rich in 2-butylene component;
(2) under the existence of alkene exchange catalysts, be rich in 2-butylene component and ethene carries out alkene permutoid reaction by described, make at least part of 2-butylene be converted to propylene, and exchange product from alkene and isolate propylene and butane; And/or
Under the existence of catalyst for cracking, the described 1-butylene component that is rich in is carried out catalytic cracking reaction, makes at least part of 1-butylene be converted into propylene, and from catalytic cracking reaction products, isolate propylene and butane;
(3) will from step (1) isolated described below C3 component with to exchange product isolated butane from alkene and/or isolated butane carries out steam cracking reaction from catalytic cracking reaction products.
The component of described liquefied petroleum gas (LPG) is known to the skilled person, as a rule, main containing C4 component in described liquefied petroleum gas (LPG), also may contain a small amount of below C3 component and/or more than C5 component.Wherein, below C3 component, in addition may containing a small amount of hydrogen, methane and C2 component mainly containing propane.C4 component, in addition may containing a small amount of iso-butylene and micro-divinyl mainly containing normal butane, Trimethylmethane, n-butene.Wherein, n-butene comprises 1-butylene and 2-butylene, and 2-butylene comprises maleic and anti-butylene.More than C5 component is mainly pentane.According to the difference in source, may there is larger difference in the content of liquefied petroleum gas (LPG) said components.
Be specially adapted in liquefied petroleum gas (LPG) of the present invention containing below C3 component, Trimethylmethane, normal butane, 1-butylene, 2-butylene and more than C5 component; And with the total content of described liquefied petroleum gas (LPG) for benchmark, the content of described below C3 component is 5-10mol%, the content of described Trimethylmethane is 5-30mol%, the content of described normal butane is 10-60mol%, the content of described 1-butylene is 10-60mol%, the content of described 2-butylene is 10-60mol%, and the content of described more than C5 component is 0.1-5mol%.
The present invention to by below C3 component, be rich in 1-butylene component and be rich in the method that 2-butylene component separates from described liquefied petroleum gas (LPG) and be not particularly limited, such as, can adopt conventional distillation, extracting rectifying, fractionation by adsorption with in chemical separation method any one or to be multiplely separated.
According to a kind of embodiment of the present invention, when containing below C3 component in described liquefied petroleum gas (LPG), Trimethylmethane, normal butane, 1-butylene, iso-butylene, when 2-butylene and more than C5 component, first be separated below C3 component and more than C4 Component seperation by conventional distillation, and more than the C4 component obtained is carried out conventional distillation separation, obtain the mixture of Trimethylmethane and 1-butylene and iso-butylene and the mixture of normal butane and 2-butylene and more than C5 component, again Trimethylmethane is carried out conventional distillation with 1-butylene and the mixture of iso-butylene and be separated the mixture and Trimethylmethane that obtain 1-butylene and iso-butylene, normal butane and 2-butylene and more than C5 component mixture are carried out conventional distillation and is separated the mixture and more than C5 component that obtain normal butane and 2-butylene.Due to 1-butylene and iso-butylene boiling point close, normal butane and 2-butylene boiling point close, use conventional distillation be separated be difficult to they are separated, also need to be separated with C 4 fraction fractionation and/or extraction fractional distillation further.
Described C 4 fraction fractionation can be under etherification reaction condition, the mixture of 1-butylene and iso-butylene and methyl alcohol are reacted, make isobutene conversion wherein be methyl tertiary butyl ether (MTBE), and then etherification product is carried out conventional distillation separation, obtain 1-butylene.
Extraction fractional distillation is the principle that utilizes the alkene of C4 and alkane relative volatility in extraction solvent to differ greatly and realizes being separated of alkane and alkene.Extraction smart process in solvent used usually can be in morpholine, N-Methyl pyrrolidone (NMP) and dimethyl formamide (DMF) any one or multiple.At present, extraction fractional distillation can be such as Japanese auspicious father-in-law's extraction fractional distillation or German Krupp-cooper that method (see DE3532289A1).
Particularly, the auspicious father-in-law's extraction fractional distillation of Japan can use DMF and/or NMP as solvent, the extracting system adopted generally includes two extracting rectifying devices and two rectifying tower, and each extracting rectifying device is made up of an extractive distillation column and a solvent recovery tower.The product obtained by first extracting rectifying device removing alkane, and is isolated 2-butylene at the first rectifying tower by C4 component, isolates 1-butylene at Second distillation column.In addition, the second extracting rectifying device is to isolate 1,3-butadiene.Therefore, if not containing 1,3-butadiene in C4 component to be separated, then the second extracting rectifying device can omit.The processing parameter of each extracting rectifying device and rectifying tower is set to as well known to those skilled in the art above, will repeat no more at this.
Germany's your method of Krupp-cooper take n-butene as target product, and raw material is C4 component after etherificate or through etherificate and precise distillation isolates the C4 component after 1-butylene and Trimethylmethane, the solvent adopted is anhydrous morpholine.Particularly, C4 component being introduced fills in the extraction solvent distillation tower of solvent, alkane in C4 component flows out from extraction solvent overhead, and the extraction liquid containing alkene goes out from extraction solvent distillation tower tower bottom flow, and the described extraction liquid containing alkene is obtained olefin component after recycling design in solvent recovery tower.The processing parameter of above extraction solvent distillation tower and solvent recovery tower is set to as well known to those skilled in the art, will repeat no more at this.
According to the present invention, as mentioned above, from described liquefied petroleum gas (LPG), the content of the isolated 1-butylene be rich in 1-butylene component is greater than 20 % by weight, the content being rich in the 2-butylene in 2-butylene component is greater than 20 weight, but in order to improve the yield of propylene, under preferable case, described in be rich in 1-butylene in 1-butylene component content be 40-100 % by weight, described in be rich in 2-butylene in 2-butylene component content be 40-100 % by weight.
According to the present invention, the condition optimization of described alkene permutoid reaction makes at least 75%, more preferably makes the 2-butylene of 80-90% be converted into propylene, can improve the yield of propylene so more significantly.In addition, at 100-600 DEG C, described in be rich in 2-butylene component and exist with the form of gas under lower pressure (as 0.01-0.5MPa), and to exist in fluid form under higher pressure (as 1-3MPa).Correspondingly, in alkene exchange procedure, the described 2-butylene component that is rich in can be reacted with the form of gas at lower pressures, also can react in fluid form at a higher pressure.Particularly, the condition that described alkene exchanges comprises: temperature of reaction can be 100-600 DEG C, preferably 120-540 DEG C, and the mol ratio of ethene and 2-butylene can be 0.5-2, be preferably 0.7-1.3; For gas-phase reaction, reaction pressure can be 0.01-0.5MPa, be preferably 0.01-0.2MPa, and during gas, volume space velocity GHSV can be 100-1000h
-1, be preferably 300-800h
-1; For liquid phase reaction, reaction pressure can be 1-3MPa, preferably 1-2MPa, and during liquid, mass space velocity can be 0.5-20h
-1, be preferably 0.5-5h
-1.
In the present invention, during described liquid, mass space velocity refers to the quality of the catalyzer of unit mass treatment solution phase reaction per hour thing.During described gas, volume space velocity refers to the volume of the catalyzer of unit volume process vapor-phase reactant per hour.Described pressure all refers to gauge pressure.
The consumption of the present invention to described alkene exchange catalysts is not particularly limited, can come reasonably to select according to the described content being rich in 2-butylene in 2-butylene component, as a rule, to be rich in described in 100 weight parts in 2-butylene component, 2-butylene is for benchmark, and the consumption of described alkene exchange catalysts can be 0.05-20 weight part.
According to the present invention, described alkene exchange catalysts can carry out for existing various 2-butylene and the ethene of can making the catalyzer that alkene permutoid reaction generates propylene, and as a rule, described alkene exchange catalysts comprises carrier and the active ingredient of load on carrier.Wherein, described carrier can be heat-resistant inorganic oxide and/or molecular sieve.Described heat-resistant inorganic oxide can be such as one or more in magnesium oxide, aluminum oxide, silicon oxide etc.Described molecular sieves is as being one or more in Y zeolite, β zeolite, mordenite, SAPO Series Molecules sieve, ZSM Series Molecules sieve, MCM Series Molecules sieve etc.Described active ingredient can be such as oxide compound and/or the sulfide of IVB race element and/or the VIIth B race element.The example of described IVB race element includes but not limited to: at least one in titanium (Ti), zirconium (Zr) and hafnium (Hf).The example of described VIIth B race element includes but not limited to: manganese (Mn) and/or rhenium (Re).
In addition, the content of described carrier and active ingredient can be the routine selection of this area, and such as, the weight ratio of described active ingredient and carrier can be 0.0001-0.2:1, is preferably 0.0001-0.1:1.
According to the present invention, the condition optimization of described catalytic cracking reaction makes at least 30%, more preferably makes the 1-butylene of 30-40% be converted into propylene, can improve the yield of propylene so more significantly.Particularly, the condition of described catalytic cracking reaction comprises: temperature of reaction can be 400-650 DEG C, and reaction pressure can be 0.07-0.5MPa, and during gas, volume space velocity can be 0.5-100h
-1, water vapor can be 0-10 with the weight ratio being rich in 1-butylene component.In described catalytic cracking reaction process, the use of water vapour can prevent the high-temperature coking of hydro carbons.
The consumption of the present invention to described catalyst for cracking is not particularly limited, can come reasonably to select according to the described content being rich in 1-butylene in 1-butylene component, as a rule, to be rich in described in 100 weight parts in 1-butylene component, 1-butylene is for benchmark, and the consumption of described catalyst for cracking can be 0.05-20 weight part.
According to the present invention, described catalyst for cracking can be the existing various catalyzer that 1-butylene catalytic pyrolysis can be made to become propylene, as a rule, described catalyst for cracking can be unmodified molecular sieve and/or heat-resistant inorganic oxide, also can be the molecular sieve of modification and/or heat-resistant inorganic oxide.Wherein, the example of modifying element includes but not limited to: one or more in phosphorus, lanthanum, cerium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, cadmium, zirconium, molybdenum, tungsten and aluminium.Described heat-resistant inorganic oxide can be such as one or more in magnesium oxide, aluminum oxide, silicon oxide etc.Described molecular sieves is as being one or more in Y zeolite, β zeolite, mordenite, SAPO Series Molecules sieve, ZSM Series Molecules sieve, MCM Series Molecules sieve etc.
In addition, the present invention is not particularly limited the content of modifying element in modified molecular screen and modified heat resistant inorganic oxide, such as, with the gross weight of modified molecular screen and modified heat resistant inorganic oxide for benchmark, the content of modifying element can be 1-10 % by weight, is preferably 1-5 % by weight.It should be noted that, when only containing modified molecular screen in described catalyst for cracking, the gross weight of described modified molecular screen and modified heat resistant inorganic oxide refers to the weight of modified molecular screen; When only containing modified heat resistant inorganic oxide in described catalyst for cracking, the gross weight of described modified molecular screen and modified heat resistant inorganic oxide refers to the weight of modified heat resistant inorganic oxide; When containing modified molecular screen and modified heat resistant inorganic oxide in described catalyst for cracking simultaneously, the gross weight of described modified molecular screen and modified heat resistant inorganic oxide refers to the weight sum of modified molecular screen and modified heat resistant inorganic oxide.
According to the present invention, existing method can be adopted propylene and butane to be separated from alkene exchange product and/or catalytic cracking reaction products, specifically according to any one in conventional distillation mentioned above, extracting rectifying, fractionation by adsorption and chemical separation or multiplely can to carry out, will repeat no more at this.
According to the present invention, the method also comprises isolates butane from liquefied petroleum gas (LPG), and will from liquefied petroleum gas (LPG) isolated butane and below C3 component and to exchange product isolated butane from alkene and/or carry out steam cracking reaction together with isolated butane from catalytic cracking reaction products.
According to the present invention, by butane isolated in liquefied petroleum gas (LPG), below C3 component and from when alkene to exchange product isolated butane and/or isolated butane carries out steam cracking reaction from catalytic cracking reaction products, can by above-mentioned they carry out steam cracking reaction respectively; Also by wherein both carry out steam cracking reaction after mixing arbitrarily, and remaining component can be carried out steam cracking reaction; Steam cracking reaction is carried out together after they can also being mixed.
Method provided by the invention also comprises isolates propylene from steam cracking product.It should be noted that, the present invention is by butane isolated in liquefied petroleum gas (LPG), below C3 component and to exchange product isolated butane from alkene and/or isolated butane carries out steam cracking reaction from catalytic cracking reaction products, multiple split product may be obtained, now, first can isolate propylene again from the mixture obtained by after multiple split product mixing, also several split product can be separated respectively.
According to the present invention, described steam cracking reaction and being separated in cracker of split product are carried out.Described cracker comprises pyrolyzer and tripping device.Described pyrolyzer can be the pyrolyzer of the steam cracking propylene that this area routine uses.Described pyrolyzer mainly comprises convection zone, radiation section, quenching boiler and gas burning system usually.In described pyrolyzer, respectively by cracking stock be steam heated to generation steam cracking reaction, generate containing the splitting gas of propylene.In the preferred case, described pyrolyzer is preferably tube cracking furnace.Described tube cracking furnace comprises convection zone, radiation section, quenching boiler and gas burning system, and cracking stock enters radiation section in convection zone; In radiation section, cracking stock be steam heated to generation steam cracking reaction, generate containing the splitting gas of propylene; Splitting gas out enters quenching boiler afterwards from radiation section, and in quenching boiler, splitting gas is cooled to 300-600 DEG C, to make splitting gas scission reaction not occur, reclaims heat simultaneously; Fuel system is used for providing heat to steam cracking reaction process.Described tripping device is used for hydrocarbon splitting gas being separated into different carbon number.As a rule, described tripping device mainly comprises: oil scrubber, water wash column, ice chest, compressor, demethanizing tower, deethanizing column, ethylene rectification tower, depropanizing tower, propylene rectification tower, debutanizing tower, C2 and C3 hydrogenation unit, C2 and C3 rectifying tower, methanation device and butadiene extraction unit.The implementation method of described tripping device has been conventionally known to one of skill in the art, does not repeat them here.
According to the present invention, when described steam cracking reaction carries out in pyrolyzer, in described steam cracking reaction process, the coil outlet temperature of described pyrolyzer is preferably 790-839 DEG C, and water weight of oil is than being preferably 0.3-1.In addition, in described steam cracking reaction process, other Parameter Conditions of described pyrolyzer can processing condition conveniently be implemented, and are not particularly limited in the present invention.
Below will be described the present invention by embodiment.
In the following Examples and Comparative Examples, the yield of propylene is according to following formulae discovery:
Gross weight × 100% of the weight ÷ steam cracking reaction product of propylene in propene yield (% by weight)=steam cracking reaction product.
In following examples and comparative example, the composition of the liquefied petroleum gas (LPG) LPG used is as shown in table 1:
Table 1
Embodiment 1
This embodiment is for illustration of the preparation method of propylene provided by the invention.
(1) be separated:
Be separated from the middle part introducing C3 tower of C3 tower with inlet amount 100kg/h, temperature 40 DEG C, pressure 11atm by liquefied petroleum gas (LPG) LPG, the material that C3 column overhead obtains is below C3 component, obtains more than C4 component at the bottom of C3 tower tower; More than C4 component introduced C4 tower from the middle part of C4 tower and be separated, the material that C4 column overhead obtains is introduced butylene tower from the middle part of butylene tower and is separated.Wherein, the parameter of C3 tower, C4 tower and butylene tower is arranged by table 2, and result is as shown in table 3.The material obtained at the bottom of butylene tower tower is raw material 1, and the material that butylene column overhead obtains to be the material obtained at the bottom of raw material 2, C4 tower tower be material that raw material 3, C4 column overhead obtains is the material that raw material 4, C3 column overhead obtains is raw material 5.
Table 2
| Numbering | C3 tower | C4 tower | Butylene tower |
| Number of theoretical plate | 35.0 | 99.0 | 150.0 |
| Tower top temperature, DEG C | 26.8 | 38.2 | 31.99 |
| Column bottom temperature, DEG C | 76.0 | 58.1 | 39.31 |
| Tower top pressure, atm | 10.0 | 4.5 | 4.0 |
| Tower bottom pressure, atm | 10.1 | 6.0 | 4.5 |
| Reflux ratio | 20.0 | 20.0 | 20.0 |
Table 3
(2) alkene permutoid reaction:
Alkene exchange catalysts comprises gamma-aluminium oxide carrier and the active ingredient Re of load on gamma-aluminium oxide carrier
2o
7, and with the gross weight of described alkene exchange catalysts for benchmark, active ingredient Re
2o
7content be 10 % by weight, the content of gamma-aluminium oxide carrier is 90 % by weight.
Loaded by alkene exchange catalysts in fixed-bed reactor (purchased from Haian Oil Scientific Research Apparatus Co., Ltd., model is WYF-2 type, lower same), the loadings of alkene exchange catalysts is 100mL.And the raw material 3 that step (1) obtains is passed in above-mentioned fixed-bed reactor continuously carry out alkene permutoid reaction, control reaction conditions is as follows: temperature of reaction is 120 DEG C, reaction pressure is 0.07MPa, and the mol ratio of ethene and 2-butylene is 1.05, and during gas, volume space velocity is 300h
-1, obtain alkene and exchange product.Wherein, the transformation efficiency of 2-butylene is 90%, and the selectivity of propylene is 94.44%.Again described alkene is exchanged product and carry out rectifying separation, obtain propylene and normal butane.
(3) catalytic cracking reaction:
Catalyst for cracking is the little crystal grain catalyzer (particle diameter is less than 800nm) with phosphorus and lanthanum modification, wherein, containing phosphorus, lanthanum, ZSM-5 molecular sieve, (silica alumina ratio is 100, particle diameter is 500nm, lower same) and silicon oxide, and with the gross weight of described catalyst for cracking for benchmark, the content of phosphorus is 5 % by weight, the content of lanthanum is 2 % by weight, the content of ZSM-5 molecular sieve is 64 % by weight, and the content of silicon oxide is 29 % by weight.
Loaded by catalyst for cracking in fixed-bed reactor (purchased from Haian Oil Scientific Research Apparatus Co., Ltd., model is WYF-2 type, lower same), the loadings of catalyst for cracking is 100mL.And the raw material 4 that step (1) obtains is passed in above-mentioned fixed-bed reactor continuously carry out olefin cracking reaction, control reaction conditions as follows: temperature of reaction is 550 DEG C, and reaction pressure is 0.15MPa, and during gas, volume space velocity is 3h
-1, obtain olefin cracking reaction product.Wherein, the transformation efficiency of 1-butylene is 70%, and the selectivity of propylene is 47.17%.Again described olefin cracking reaction product is carried out rectifying separation, obtain propylene and Trimethylmethane.
(4) steam cracking reaction:
The Trimethylmethane that normal butane step (2) obtained, step (3) obtain and raw material 5 are introduced in pyrolyzer respectively and are carried out steam cracking reaction, obtain three kinds of steam cracking products.Wherein, the condition of steam cracking reaction is as shown in table 4 below.Isolate propylene after being mixed by three kinds of steam cracking products, and calculate the yield of propylene, result is as shown in table 5.
Embodiment 2
This embodiment is for illustration of the preparation method of propylene provided by the invention.
(1) be separated:
Carry out according to the method for embodiment 1;
(2) catalytic cracking reaction:
Catalyst for cracking is with phosphorus and cerium modified little crystal grain catalyzer (particle diameter is less than 800nm), wherein, containing phosphorus, cerium, ZSM-5 molecular sieve, and with the gross weight of described catalyst for cracking for benchmark, the content of phosphorus is 5 % by weight, the content of cerium is 2 % by weight, and the content of ZSM-5 molecular sieve is 93 % by weight.
Loaded by catalyst for cracking in fixed-bed reactor, the loadings of catalyst for cracking is 100mL.And the raw material 2 that step (1) obtains is passed in above-mentioned fixed-bed reactor continuously carry out olefin cracking reaction, control reaction conditions as follows: temperature of reaction is 400 DEG C, and reaction pressure is 0.07MPa, and during gas, volume space velocity is 0.5h
-1, obtain olefin cracking reaction product 1.Wherein, the transformation efficiency of 1-butylene is 55%, and the selectivity of propylene is 48.57%.Again described olefin cracking reaction product 1 is carried out rectifying separation, obtain propylene, 1-butylene and Trimethylmethane.And then mix being separated the 1-butylene obtained from olefin cracking reaction product 1 with raw material 1, and the mixture obtained is passed in above-mentioned fixed-bed reactor continuously carry out olefin cracking reaction, reaction conditions is identical with the reaction conditions of raw material 2, obtains olefin cracking reaction product 2.Wherein, the transformation efficiency of 1-butylene is 57%, and the selectivity of propylene is 48.65%.Again described olefin cracking reaction product 2 is carried out rectifying separation, obtain propylene and Trimethylmethane.
(3) alkene permutoid reaction:
Alkene exchange catalysts comprises gamma-aluminium oxide carrier and the active ingredient TiO of load on gamma-aluminium oxide carrier
2, and with the gross weight of described alkene exchange catalysts for benchmark, active ingredient TiO
2content be 15 % by weight, the content of gamma-aluminium oxide carrier is 85 % by weight.
Loaded in fixed-bed reactor by alkene exchange catalysts, the loadings of alkene exchange catalysts is 150mL.And the raw material 3 that step (1) obtains is passed in above-mentioned fixed-bed reactor continuously carry out alkene permutoid reaction, control reaction conditions is as follows: temperature of reaction is 540 DEG C, reaction pressure is 0.7MPa, and the mol ratio of ethene and 2-butylene is 2, and during gas, volume space velocity is 800h
-1, obtain alkene and exchange product.Wherein, the transformation efficiency of 2-butylene is 95%, and the selectivity of propylene is 89.67%.Again described alkene is exchanged product and carry out rectifying separation, obtain propylene and normal butane.
(4) step (2) is separated from olefin cracking reaction product 1 and olefin cracking reaction product 2 mixture of the Trimethylmethane obtained, step (3) exchanges product the normal butane that is separated and obtains and raw material 5 from alkene and introduces in pyrolyzer respectively and carry out steam cracking reaction, obtain three kinds of steam cracking products.Wherein, the condition of steam cracking reaction is as shown in table 4 below.Isolate propylene after being mixed by three kinds of steam cracking products, and calculate the yield of propylene, result is as shown in table 5.
Embodiment 3
This embodiment is for illustration of the preparation method of propylene provided by the invention.
(1) be separated:
Carry out according to the method for embodiment 1;
(2) alkene permutoid reaction:
Alkene exchange catalysts comprises gamma-aluminium oxide carrier and the active ingredient ZrO of load on gamma-aluminium oxide carrier
2, and with the gross weight of described alkene exchange catalysts for benchmark, active ingredient ZrO
2content be 2 % by weight, the content of gamma-aluminium oxide carrier is 98 % by weight.
Loaded in fixed-bed reactor by alkene exchange catalysts, the loadings of alkene exchange catalysts is 120mL.And the raw material 3 that step (1) obtains is passed in above-mentioned fixed-bed reactor continuously carry out alkene permutoid reaction, control reaction conditions is as follows: temperature of reaction is 300 DEG C, reaction pressure is 0.07MPa, and the mol ratio of ethene and 2-butylene is 0.5, and during gas, volume space velocity is 500h
-1, obtain alkene and exchange product.Wherein, the transformation efficiency of 2-butylene is 45%, and the selectivity of propylene is 93.84%.Again described alkene is exchanged product and carry out rectifying separation, obtain propylene and normal butane.
(3) catalytic cracking reaction:
Catalyst for cracking is the little crystal grain catalyzer (particle diameter is less than 800nm) with chromium and manganese modification, wherein, containing chromium, manganese and silicon oxide, and with the gross weight of described catalyst for cracking for benchmark, the content of chromium is 5 % by weight, and the content of manganese is 2 % by weight, and the content of silicon oxide is 93 % by weight.
Loaded by catalyst for cracking in fixed-bed reactor, the loadings of catalyst for cracking is 120mL.And the raw material 4 that step (1) obtains is passed in above-mentioned fixed-bed reactor continuously carry out olefin cracking reaction, control reaction conditions as follows: temperature of reaction is 650 DEG C, and reaction pressure is 0.5MPa, and during gas, volume space velocity is 20h
-1, obtain olefin cracking reaction product.Wherein, the transformation efficiency of 1-butylene is 73%, and the selectivity of propylene is 46.89%.Again described olefin cracking reaction product is carried out rectifying separation, obtain propylene and Trimethylmethane.
(4) Trimethylmethane that normal butane step (2) obtained, step (3) obtain and raw material 5 are introduced in pyrolyzer respectively and are carried out steam cracking reaction, obtain three kinds of steam cracking products.Wherein, the condition of steam cracking reaction is as shown in table 4 below.Isolate propylene after being mixed by three kinds of steam cracking products, and calculate the yield of propylene, result is as shown in table 5.
Embodiment 4
This embodiment is for illustration of the preparation method of propylene provided by the invention.
(1) be separated:
According to the method for embodiment 1, liquefied petroleum gas (LPG) is separated, obtains raw material 1, raw material 2, raw material 3, raw material 4 and raw material 5.And then respectively raw material 3 and raw material 4 are extracted by your extraction fractional distillation of German Krupp-cooper, obtain 1-butylene, Trimethylmethane, normal butane and 2-butylene.
(2) alkene permutoid reaction:
Carry out according to the method for embodiment 1, unlike, raw material 3 2-butylene that step (1) obtains substitutes, and obtains alkene and exchanges product.Wherein, the transformation efficiency of 2-butylene is 90%, and the selectivity of propylene is 94.44%.Again described alkene is exchanged product and carry out rectifying separation, obtain propylene and normal butane.
(3) catalytic cracking reaction:
Carry out according to the method for embodiment 1, unlike, raw material 4 1-butylene that step (1) obtains substitutes, and obtains olefin cracking reaction product.Wherein, the transformation efficiency of 1-butylene is 70%, and the selectivity of propylene is 47.17%.Again described olefin cracking reaction product is carried out rectifying separation, obtain propylene and Trimethylmethane.
(4) steam cracking reaction:
The mixture of the Trimethylmethane that the mixture of normal butane step (1) and step (2) obtained, step (1) and step (3) obtain and raw material 5 are introduced in pyrolyzer respectively and are carried out steam cracking reaction, obtain three kinds of steam cracking products.Wherein, the condition of steam cracking reaction is as shown in table 4 below.Isolate propylene after being mixed by three kinds of steam cracking products, and calculate the yield of propylene, result is as shown in table 5.
Comparative example 1
This comparative example is for illustration of the reference preparation method of propylene.
Propylene is prepared according to the method for embodiment 1, unlike, this comparative example does not comprise the step of alkene permutoid reaction and catalytic cracking reaction, but direct raw material 3, raw material 4 and raw material 5 introducings in pyrolyzer respectively carries out steam cracking reaction, obtains three kinds of steam cracking products.Wherein, the condition of steam cracking reaction is as shown in table 4 below.Isolate propylene after being mixed by three kinds of steam cracking products, and calculate the yield of propylene, result is as shown in table 5.
Comparative example 2
This comparative example is for illustration of the reference preparation method of propylene.
Propylene is prepared according to the method for embodiment 2, unlike, this comparative example does not comprise the step of alkene permutoid reaction and catalytic cracking reaction, but direct raw material 1, raw material 2, raw material 3 and raw material 5 introducings in pyrolyzer respectively carries out steam cracking reaction, obtains four kinds of steam cracking products.Wherein, the condition of steam cracking reaction is as shown in table 4 below.Isolate propylene after being mixed by four kinds of steam cracking products, and calculate the yield of propylene, result is as shown in table 5.
Comparative example 3
This comparative example is for illustration of the reference preparation method of propylene.
Liquefied petroleum gas (LPG) LPG is introduced in pyrolyzer and carries out steam cracking reaction, and isolate propylene from the steam cracking product obtained.Wherein, the condition of steam cracking reaction is as shown in table 4 below, and result is as shown in table 5.
Table 4
Note: in table 4, CBL-III type pyrolyzer and CBL-R type pyrolyzer are all purchased from China PetroChemical Corporation.
Table 5
| Numbering | Cracking stock | Propene yield (% by weight) |
| Embodiment 1 | Normal butane+Trimethylmethane+raw material 5 | 40.56 |
| Embodiment 2 | Normal butane+Trimethylmethane+raw material 5 | 38.95 |
| Embodiment 3 | Normal butane+Trimethylmethane+raw material 5 | 30.34 |
| Embodiment 4 | Normal butane+Trimethylmethane+raw material 5 | 39.96 |
| Comparative example 1 | Raw material 3+ raw material 4+ raw material 5 | 23.54 |
| Comparative example 2 | Raw material 1+ raw material 2+ raw material 3+ raw material 5 | 24.58 |
| Comparative example 3 | LPG | 18.26 |
As can be seen from the above results, adopt method provided by the invention can significantly improve the yield of propylene, thus solve existing liquefied petroleum gas (LPG) utilization ratio and the low problem of Economic Value Added.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (15)
1. a preparation method for propylene, the method comprises the following steps:
(1) from liquefied petroleum gas (LPG), isolate below C3 component, 1-butylene content be more than 20 % by weight be rich in 1-butylene component, 2-butylene content be more than 20 % by weight be rich in 2-butylene component;
(2) under the existence of alkene exchange catalysts, be rich in 2-butylene component and ethene carries out alkene permutoid reaction by described, make at least part of 2-butylene be converted to propylene, and exchange product from alkene and isolate propylene and butane; And/or
Under the existence of catalyst for cracking, the described 1-butylene component that is rich in is carried out catalytic cracking reaction, makes at least part of 1-butylene be converted into propylene, and from catalytic cracking reaction products, isolate propylene and butane;
(3) will from step (1) isolated described below C3 component with to exchange product isolated butane from alkene and/or isolated butane carries out steam cracking reaction from catalytic cracking reaction products.
2. method according to claim 1, wherein, containing below C3 component, Trimethylmethane, normal butane, 1-butylene, 2-butylene and more than C5 component in described liquefied petroleum gas (LPG); And with the total content of described liquefied petroleum gas (LPG) for benchmark, the content of described below C3 component is 5-10mol%, the content of described Trimethylmethane is 5-30mol%, the content of described normal butane is 10-60mol%, the content of described 1-butylene is 10-60mol%, the content of described 2-butylene is 10-60mol%, and the content of described more than C5 component is 0.1-5mol%.
3. method according to claim 1 and 2, wherein, described in be rich in 1-butylene in 1-butylene component content be 40-100 % by weight, described in be rich in 2-butylene in 2-butylene component content be 40-100 % by weight.
4. method according to claim 1 and 2, wherein, the condition of described alkene permutoid reaction makes the 2-butylene of at least 75% be converted into propylene.
5. method according to claim 4, wherein, the condition of described alkene permutoid reaction makes the 2-butylene of 80-90% be converted into propylene.
6. method according to claim 4, wherein, the condition of described alkene permutoid reaction comprises: temperature of reaction is 100-600 DEG C, the mol ratio of ethene and 2-butylene is 0.5-2, for gas-phase reaction, reaction pressure is 0.01-0.5MPa, and during gas, volume space velocity is 100-1000h
-1; For liquid phase reaction, reaction pressure is 1-3MPa, and during liquid, mass space velocity is 0.5-20h
-1.
7. method according to claim 4, wherein, described alkene exchange catalysts comprises carrier and the active ingredient of load on carrier, described carrier is heat-resistant inorganic oxide and/or molecular sieve, and described active ingredient is oxide compound and/or the sulfide of IVB race element and/or the VIIth B race element.
8. method according to claim 7, wherein, the weight ratio of described active ingredient and carrier is 0.0001-0.2:1.
9. method according to claim 1 and 2, wherein, the condition of described catalytic cracking reaction makes the 1-butylene of at least 30% be converted into propylene.
10. method according to claim 9, wherein, the condition of described catalytic cracking reaction makes the 1-butylene of 30-40% be converted into propylene.
11. methods according to claim 9, wherein, the condition of described catalytic cracking reaction comprises: temperature of reaction is 400-650 DEG C, and reaction pressure is 0.07-0.5MPa, and during gas, volume space velocity is 0.5-100h
-1, water vapor is 0-10 with the weight ratio being rich in 1-butylene component.
12. methods according to claim 9, wherein, described catalyst for cracking is modification or unmodified molecular sieve and/or heat-resistant inorganic oxide, and 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.
13. methods according to claim 12, wherein, with the gross weight of modified molecular screen and modified heat resistant inorganic oxide for benchmark, the content of modifying element is 1-10 % by weight.
14. methods according to claim 2, wherein, the method also comprises isolates butane from liquefied petroleum gas (LPG), and will from liquefied petroleum gas (LPG) isolated butane and below C3 component and to exchange product isolated butane from alkene and/or carry out steam cracking reaction together with isolated butane from catalytic cracking reaction products.
15. methods according to claim 1,2 or 14, wherein, described steam cracking reaction carries out in pyrolyzer, and in described steam cracking reaction process, the coil outlet temperature of described pyrolyzer is 790-839 DEG C, and water weight of oil is than being 0.3-1.
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| CN202936328U (en) * | 2012-09-07 | 2013-05-15 | 李绍通 | Optimizing facility for preparing propylene by catalytic cracking of mixed butylene |
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| US6777582B2 (en) * | 2002-03-07 | 2004-08-17 | Abb Lummus Global Inc. | Process for producing propylene and hexene from C4 olefin streams |
| CN202936328U (en) * | 2012-09-07 | 2013-05-15 | 李绍通 | Optimizing facility for preparing propylene by catalytic cracking of mixed butylene |
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