CN104250198A - Butadiene preparation method - Google Patents
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Abstract
The invention provides a butadiene preparation method which comprises (1) separation of hydrocarbon components with the 1-butene content of more than 10wt% from liquefied petroleum gas; (2) isomerization reaction of the hydrocarbon components in the presence of an isomerization catalyst t for isomerization of at least part of 1-butene into 2-butene to obtain isomerization products; and (3) steam cracking reaction of the isomerization products. The method can obtain high butadiene yield, and utilization ratio and economic added value of the liquefied petroleum gas can be improved.
Description
Technical field
The present invention relates to a kind of preparation method of divinyl.
Background technology
Divinyl typically refers to 1,3-butadiene, also known as ethylene vinyl, is the important basic petrochemical raw material being only second to ethene and propylene.Divinyl is mainly used in synthetic rubber and resin, as polybutadiene rubber (BR), styrene-butadiene rubber(SBR) (SBR), paracril (NBR), styrene-butadiene polymer latex, styrenic thermoplastic elastomer (SBC) and acrylonitrile-butadiene-styrene (ABS) (ABS) resin etc.In addition, divinyl for the production of Organic chemical products such as adiponitrile, hexanediamine, nylon-66, BDOs, can also be widely used in numerous areas.
The industrial process of divinyl successively experienced by alcohol dehydrogenase method, butylene catalytic dehydrogenation methods, catalytic dehydrogenation of butanes method, butylene oxidation-dehydrogenation method and ethylene by-product C 4 fraction partition method.At present, the source of divinyl raw material mainly contains two kinds: the hybrid C 4 cut of ethylene cracker by-product and refinery C 4 fraction.In the butadiene production in the whole world, 92% comes from ethylene by-product C 4 fraction partition method, 8% dehydriding coming from normal butane dehydriding and n-butene.
Wherein, ethylene by-product C 4 fraction partition method is cheap because of it, has larger economic advantages, becomes the main production process of divinyl.Owing to using the difference of solvent, the C 4 fraction separation of produced divinyl of ethylene unit by-product has following methods: furfural method, acetonitrile method, dimethyl formamide method, N,N-DIMETHYLACETAMIDE method, N methylpyrrolidone process etc.At present, competitive with acetonitrile method (ACN) most of the N methylpyrrolidone process (NMP) of the dimethyl formamide method (DMF) of Nippon Zeon Co., Ltd., BASF Corp. of Germany and the improvement of Japanese JSR company.These technological processs are substantially identical, contacted by the C 4 fraction from ethylene unit with extraction solvent, and the butenes/butanes blending ingredients of indissoluble removes from tower top, then remove extraction solvent from taking out excess by the method for simple distillation.Afterwards by distilling impurity removals such as acetylene further, obtain the divinyl that purity is 99.5-99.9%.In various extraction process, NMP method has the advantages such as flow process is relatively simple, cost of investment is lower, easy to operate, better economic benefit.In addition, C 4 fraction selec-tive hydrogenation is except novel process constantly development and application such as alkynes techniques (being called for short KLP technique).
In recent years, American UOP and BASF AG's joint development go out extracting process integration, namely, the selective acetylene hydrocarbon hydrogenation technique (KLP technique) of UOP and the Butadiene Extraction distil process of BASF AG are combined, first by the selective acetylene hydrocarbon hydrogenation in C 4 fraction, then extractive distillation technology is adopted to reclaim 1,3-butadiene from butane and butylene.In hydrogenation process, raw material C 4 fraction mixes with the hydrogen necessarily measured, and enters in the fixed-bed reactor that KLP-60 catalyzer is housed, and adopts sufficiently high pressure to make reaction mixture keep liquid phase.KLP reactor effluent enters in distillation tower and vaporizes subsequently, and as the raw material of extraction process, removes a small amount of heavy ends formed in technological process simultaneously.In Butadiene Extraction operation, from vaporizer top, steam out enters main washing tower, and carries out extractive distillation with NMP.The logistics being rich in divinyl at the bottom of tower enters rectifying tower, and then enters last distillation tower, can the output purity 1,3-butadiene that is greater than 99.6%.The divinyl purity that the advantage of this technique obtains is high, yield is high, utility cost is low, maintenance cost is low and processing safety is high.
In addition, Mitsubishi chemical company announced in March, 2009, and it utilizes the proprietary catalyzer of independent research, develops new technology butylene little for purposes being converted to 1,3-butadiene.This technological process completes pilot scale (ability is 200 tons/year) in production base, Mitsubishi Chemical Ind's Japanese water island.The said firm completed technological design in 2009, was intended to make this technology push commercial applications in 2010.
In recent years, research about butadiene production technology focuses mostly in the improvement of C 4 fraction extraction process, as Beijing Chemical Research Institute to propose a kind of novel process (see CN101665399A) of butadiene production in 2009, except selec-tive hydrogenation is combined with extractive distillation technique, also degassing tower is set at extraction overhead extraction place, isolate the remaining hydrogen after hydrogenation reaction and below C4 light constituent, avoid losing divinyl.In the raw material producing divinyl, the heals being rich in alkynes that PetroChina Company Ltd. obtains after proposing to utilize Butadiene Extraction in 2009 carries out selec-tive hydrogenation and obtains divinyl (see CN101434508A).
At present, on divinyl Downstream Market, the demand of rubber and ABS resin is continuing to increase, divinyl consumption with average annual about 10% speed increment, and production capacity expansion rate of increase less than 8%, the production of divinyl is still in the state that supply falls short of demand.In the preparation technology of traditional divinyl, the traditional raw material of steam-cracking process is mainly based on lighter hydrocarbons, petroleum naphtha, hydrogenation tail oil.But the butadiene yield of lighter hydrocarbons steam cracking is less than 3%, the butadiene yield of naphtha steam cracking is 3-6%, and the butadiene yield of hydrogenation tail oil steam cracking is 4-7%.Therefore with traditional raw material volume increase divinyl approach be very limited.So, constantly expand butadiene production approach, exploitation new raw material and variation route, for ethylene unit and divinyl industry necessary.
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) (being called for short 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 divinyl is provided, adopt the method can obtain higher butadiene yield.
The invention provides a kind of preparation method of divinyl, the method comprises the following steps:
(1) from liquefied petroleum gas (LPG), isolate the hydrocarbon component that 1-butylene content is more than 10 % by weight;
(2) under the existence of isomerization catalyst, described hydrocarbon component is carried out isomerization reaction, make at least part of 1-butylene wherein be isomerizated into 2-butylene, obtain isomerization product;
(3) described isomerization product is carried out steam cracking reaction.
As can be seen from the result of embodiment, adopt method provided by the invention that the yield of divinyl can be made to reach more than 9.27%, that is, relatively high butadiene yield can be obtained, 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 divinyl provided by the invention comprises the following steps:
(1) from liquefied petroleum gas (LPG), isolate the hydrocarbon component that 1-butylene content is more than 10 % by weight;
(2) under the existence of isomerization catalyst, described hydrocarbon component is carried out isomerization reaction, make at least part of 1-butylene wherein be isomerizated into 2-butylene, obtain isomerization product;
(3) described isomerization product is carried out steam cracking reaction.
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 can be 0.1-10mol%, the content of described Trimethylmethane can be 5-20mol%, the content of described normal butane can be 5-30mol%, the content of described 1-butylene can be 20-40mol%, the content of described 2-butylene can be the content of 20-50mol%, more than C5 component can be 0.1-5mol%.Under preferable case, with the total content of described liquefied petroleum gas (LPG) for benchmark, the content of described below C3 component can be 5-10mol%, the content of described Trimethylmethane can be 5-15mol%, the content of described normal butane can be 10-30mol%, the content of described 1-butylene can be 25-35mol%, and the content of described 2-butylene can be the content of 25-40mol%, more than C5 component can be 0.1-0.5mol%.
According to the present invention, in order to improve the productive rate of divinyl more significantly, with the gross weight of described hydrocarbon component for benchmark, in described hydrocarbon component, the content of 1-butylene is preferably 15-100 % by weight, is more preferably 30-100 % by weight.
The present invention is not particularly limited the method isolating hydrocarbon component from liquefied petroleum gas (LPG), 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 in described liquefied petroleum gas (LPG) containing below C3 component (as ethane, propane and propylene), normal butane, Trimethylmethane, 1-butylene, 2-butylene and more than C5 component time, first pass through conventional distillation method by below C3 component and more than C4 Component seperation, described more than C4 component is the mixture of normal butane, Trimethylmethane, 1-butylene, 2-butylene and more than C5 component.Further, the mixture of above-mentioned normal butane, Trimethylmethane, 1-butylene, 2-butylene and more than C5 component further rectifying separation be can also be carried out again, the mixture of Trimethylmethane and 1-butylene and iso-butylene and the mixture of normal butane and 2-butylene and more than C5 component obtained.Further, again Trimethylmethane conventional distillation be can also be carried out with 1-butylene and the mixture of iso-butylene and the mixture and Trimethylmethane that obtain 1-butylene and iso-butylene are separated; 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.Because the boiling point of 1-butylene and iso-butylene is close, the boiling point of normal butane and 2-butylene is close, use conventional distillation to be separated and be difficult to them to separate, if need them to be separated further, also need to be separated with C 4 fraction fractionation and/or extraction fractional distillation.
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, 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, when the content of 2-butylene is higher in described isomerization product, the yield of divinyl can be improved.Therefore, in order to improve the yield of divinyl more significantly, make the 1-butylene of 20-100% in described hydrocarbon component be isomerizated into 2-butylene the condition optimization that described hydrocarbon component carries out isomerization reaction, most preferably make the 1-butylene of in described hydrocarbon component 100% be isomerizated into 2-butylene.In actual production process, an isomerization reaction possibly cannot make the 1-butylene in described hydrocarbon component all be converted into 2-butylene, now, isomerization product can be separated, obtain 1-butylene and 2-butylene, returning in isomerization reaction step by being separated the 1-butylene obtained again, repeating this step if desired.
Particularly, the condition of described isomerization reaction comprises temperature of reaction, reaction pressure and mass space velocity.In order to more be conducive to the carrying out of isomerization reaction, it can be 0-550 DEG C that the condition optimization of described isomerization reaction comprises temperature of reaction, and reaction pressure can be-0.08MPa to 10MPa, and mass space velocity can be 0.1-100h
-1; More preferably comprising temperature of reaction is 50-480 DEG C, and reaction pressure is 0-3.5MPa, and mass space velocity is 0.1-20h
-1.
Wherein, because hydrocarbon component may be liquid phase under different temperature and pressures, also may be gas phase, therefore, mass space velocity when mass space velocity described herein can be liquid, mass space velocity when also can be gas, specifically refers to the quality of the catalyzer of unit mass processing hydrocarbons component per hour.
The consumption of the present invention to described isomerization catalyst is not particularly limited, can come reasonably to select according to the content of 1-butylene in described hydrocarbon component, particularly, with the 1-butylene of 100 weight parts for benchmark, the consumption of described isomerization catalyst can be 0.001-10 weight part.
The kind of the present invention to described isomerization catalyst is not particularly limited, as long as at least part of 1-butylene in described hydrocarbon component can be converted into 2-butylene, such as, described isomerization catalyst can be one or more in IA family metal oxide, IIA family metal oxide and VIIIA race metal.
Particularly, the example of described IA family metal oxide can include but not limited to: one or more in Lithium Oxide 98min, sodium oxide, potassium oxide etc.The example of described IIA family metal oxide can include but not limited to: one or more in magnesium oxide, calcium oxide, strontium oxide, barium oxide, radium oxide etc.The example of described group VIII metal can include but not limited to: one or more in iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium and platinum etc.
One or more in above-mentioned IA family metal oxide, IIA family metal oxide and group VIII metal can be used alone as isomerization catalyst, also first load can be used as isomerization catalyst afterwards 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 sieve can be pure silicon molecular sieve, also can be silica alumina ratio SiO
2/ Al
2o
3the crystal aluminosilicate of=5-1000.Described crystal aluminosilicate can be selected from Y zeolite, β zeolite, mordenite, SAPO Series Molecules sieve, ZSM Series Molecules sieve, MCM Series Molecules sieve etc. one or more.
According to the present invention, under preferable case, described method also comprises carries out steam cracking reaction by petroleum hydrocarbon together with described isomerization product, can obtain relatively high butadiene yield like this.
The consumption of the present invention to described isomerization product and petroleum hydrocarbon is not particularly limited, reasonably can select according to practical situation, such as, with total consumption of described isomerization product and petroleum hydrocarbon for benchmark, the consumption of described isomerization product can be 5-99 % by weight, and the consumption of described petroleum hydrocarbon can be 1-95 % by weight; Preferably, with total consumption of described isomerization product and petroleum hydrocarbon for benchmark, the consumption of described isomerization product is 10-99 % by weight, and the consumption of described petroleum hydrocarbon is 1-90 % by weight.
The kind of described petroleum hydrocarbon is known to the skilled person, and such as, can be one or more in light hydrocarbon mixture, petroleum naphtha, diesel oil, hydrogenation tail oil etc.In the present invention, described light hydrocarbon mixture refers to 2-butylene and the C except 2-butylene
1-C
5the mixture of lighter hydrocarbons.In described light hydrocarbon mixture, with the gross weight of described light hydrocarbon mixture for benchmark, the content of described 2-butylene can be 25-99 % by weight, the C except 2-butylene
1-C
5the total content of lighter hydrocarbons can be 1-75 % by weight.
The present inventor finds, because isomerization product is combined with petroleum naphtha and/or light hydrocarbon mixture, not only can obtain higher butadiene yield, but also the coking of convection section in cracking furnace can be prevented, therefore, described petroleum hydrocarbon is particularly preferably petroleum naphtha and/or light hydrocarbon mixture.
Method provided by the invention also comprises isolates divinyl from steam cracking reaction product.
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 divinyl 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 divinyl.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 divinyl; 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 680-839 DEG C, is more preferably 760-839 DEG C; Water weight of oil, than being preferably 0.3-1, is more preferably 0.3-0.65.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 divinyl is according to following formulae discovery:
Gross weight × 100% of the weight ÷ steam cracking reaction product of divinyl in butadiene yield (% by weight)=steam cracking reaction product.
The composition of the LPG used in following examples and comparative example is as shown in table 1.
Table 1
Shown in the correlation parameter of the petroleum naphtha used in following examples and comparative example and the table 2 composed as follows that records according to ASTMD5443 method.
Table 2
The composition of the light hydrocarbon mixture used in following examples and comparative example is as shown in table 3.
Table 3
Embodiment 1
This embodiment is for illustration of the preparation method of divinyl provided by the invention.
(1) be separated:
The tripping device adopted comprises C3 tower, C4 tower and butylene tower, liquefied petroleum gas (LPG) LPG is carried out rectifying with the condition of inlet amount 1000kg/h, temperature 40 DEG C, pressure 11atm from the middle part introducing C3 tower of C3 tower, and the product obtained at the bottom of C3 tower tower is carried out rectifying separation from the middle part introducing C4 tower of C4 tower, then product C4 column overhead obtained carries out rectifying separation from the middle part introducing butylene tower of butylene tower.Each tower parameter is arranged by table 4, and the separating resulting of gained is as shown in table 5.
Table 4
| 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 | 31.9 |
| 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 5
The material obtained at the bottom of C3 tower tower is raw material 1, and wherein, the mass content of Trimethylmethane is 8.89%, the mass content 31.18% of normal butane, and the mass content of 1-butylene is 33.02%, and the mass content of 2-butylene is 26.14%, and the mass content of pentane is 0.76%; The material that C4 tower top obtains is raw material 2, and wherein, the mass content of Trimethylmethane is 21.21%, and the mass content of normal butane is 0.43%, and the mass content of 1-butylene is 78.28%, and the mass content of 2-butylene is 0.05%; The material that butylene column overhead obtains is raw material 3, and wherein, the mass content of 1-butylene is 40.40%, remaining as Trimethylmethane; The material obtained at the bottom of butylene tower tower is raw material 4, and wherein, the mass content of 1-butylene is 98.87%.
(2) isomerization reaction:
The preparation of isomerization catalyst: 1.5 grams of Lithium Oxide 98mins are added containing in 50 grams of magnesian aqueous solution, obtain 500g mixing solutions, and after by the mixing solutions obtained, at 50 DEG C, heating in water bath stirs 5 hours, moisture in suction filtration solution, again by solids yield successively 120 DEG C dry 6 hours, 550 DEG C of roastings 6 hours, obtain isomerization catalyst, wherein, the content of Lithium Oxide 98min is 3.1 % by weight.
Loaded by isomerization catalyst in fixed-bed reactor (purchased from Haian Oil Scientific Research Apparatus Co., Ltd., model is WYF-2, lower same), the loadings of isomerization catalyst is 15mL.Respectively raw material 1-4 is sent in fixed-bed reactor continuously and carry out isomerization reaction, control reaction conditions as follows: temperature of reaction is 250 DEG C, and reaction pressure is 1MPa, and mass space velocity is 4, obtains cracking stock 1-4 respectively.
Wherein, the concrete composition of cracking stock 1-4 is as shown in table 6.
Table 6
(3) steam cracking reaction:
The cracking stock 1 that step (2) obtains is injected in CBL-III type pyrolyzer (purchased from China PetroChemical Corporation, lower same) and carry out steam cracking reaction, and isolate divinyl from steam cracking reaction product.Wherein, described reaction conditions and result as shown in table 7 below.
Embodiment 2
This embodiment is for illustration of the preparation method of divinyl provided by the invention.
(1) be separated:
Carry out according to the method for embodiment 1;
(2) isomerization reaction:
Carry out according to the method for embodiment 1;
(3) steam cracking reaction:
The cracking stock 2 that step (2) obtains is injected CBL-III type pyrolyzer and carries out steam cracking reaction, and isolate divinyl from steam cracking reaction product.Wherein, described reaction conditions and result as shown in table 7 below.
Embodiment 3
This embodiment is for illustration of the preparation method of divinyl provided by the invention.
(1) be separated:
Carry out according to the method for embodiment 1;
(2) isomerization reaction:
Carry out according to the method for embodiment 1;
(3) steam cracking reaction:
The cracking stock 3 that step (2) obtains is injected CBL-III type pyrolyzer and carries out steam cracking reaction, and isolate divinyl from steam cracking reaction product.Wherein, described reaction conditions and result as shown in table 7 below.
Embodiment 4
This embodiment is for illustration of the preparation method of divinyl provided by the invention.
(1) be separated:
Carry out according to the method for embodiment 1;
(2) isomerization reaction:
Carry out according to the method for embodiment 1;
(3) steam cracking reaction:
The cracking stock 4 that step (2) obtains is injected CBL-III type pyrolyzer and carries out steam cracking reaction, and isolate divinyl from steam cracking reaction product.Wherein, described reaction conditions and result as shown in table 7 below.
Embodiment 5
This embodiment is for illustration of the preparation method of divinyl provided by the invention.
(1) be separated:
Carry out according to the method for embodiment 1;
(2) isomerization reaction:
Carry out according to the method for embodiment 1;
(3) steam cracking reaction:
The mixture (weight ratio of isomerization product and petroleum naphtha is 1:0.67) of the cracking stock 1 obtain step (2) and petroleum naphtha is introduced in CBL-III type pyrolyzer and is carried out steam cracking reaction, and isolates divinyl from steam cracking product.Wherein, the condition of steam cracking reaction and result as shown in table 7.
Embodiment 6
This embodiment is for illustration of the preparation method of divinyl provided by the invention.
Divinyl is prepared according to the method for embodiment 5, unlike, the light hydrocarbon mixture of described petroleum naphtha identical weight part substitutes.Wherein, the condition of steam cracking reaction and result as shown in table 7.
Comparative example 1
This comparative example is for illustration of the reference preparation method of divinyl.
Liquefied petroleum gas (LPG) LPG is introduced in CBL-III type pyrolyzer and carry out steam cracking reaction, and isolate divinyl from steam cracking product.Wherein, the condition of steam cracking reaction and result as shown in table 7.
Comparative example 2
This comparative example is for illustration of the reference preparation method of divinyl.
Petroleum naphtha is introduced in CBL-III type pyrolyzer and carry out steam cracking reaction, and isolate divinyl from steam cracking product.Wherein, the condition of steam cracking reaction and result as shown in table 7.
Comparative example 3
This comparative example is for illustration of the reference preparation method of divinyl.
Light hydrocarbon mixture is introduced in CBL-III type pyrolyzer and carry out steam cracking reaction, and isolate divinyl from steam cracking product.Wherein, the condition of steam cracking reaction and result as shown in table 7.
Table 7
As can be seen from the above results, the mixture that the steam crack material used in embodiment 1-6 is isomerization reaction product or isomerization product and petroleum hydrocarbon, and the steam crack material used in comparative example 1-3 is LPG or petroleum hydrocarbon, acetonideexample 1-6 obtains obviously higher butadiene yield, thus solves 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 (10)
1. a preparation method for divinyl, the method comprises the following steps:
(1) from liquefied petroleum gas (LPG), isolate the hydrocarbon component that 1-butylene content is more than 10 % by weight;
(2) under the existence of isomerization catalyst, described hydrocarbon component is carried out isomerization reaction, make at least part of 1-butylene wherein be isomerizated into 2-butylene, obtain isomerization product;
(3) described isomerization product is carried out steam cracking reaction.
2. method according to claim 1, wherein, with the total content of described hydrocarbon component for benchmark, in described hydrocarbon component, the content of 1-butylene is 15-100 % by weight.
3. method according to claim 1 and 2, wherein, the condition of described isomerization reaction makes the 1-butylene of 20-100% in described hydrocarbon component be isomerizated into 2-butylene.
4. method according to claim 3, wherein, the condition of described isomerization reaction comprises: temperature of reaction is 0-550 DEG C, reaction pressure be-0.08MPa to 10MPa, mass space velocity is 0.1-100h
-1; Preferably, the condition of described isomerization reaction comprises: temperature of reaction is 50-480 DEG C, and reaction pressure is 0-3.5MPa, and mass space velocity is 0.1-20h
-1.
5. the method according to claim 1,2 or 4, wherein, described isomerization catalyst is one or more in IA family metal oxide, IIA family metal oxide and group VIII metal.
6. method according to claim 1 and 2, wherein, the method also comprises carries out steam cracking reaction by petroleum hydrocarbon together with described isomerization product.
7. method according to claim 6, wherein, with total consumption of described isomerization product and petroleum hydrocarbon for benchmark, the consumption of described isomerization product is 5-99 % by weight, and the consumption of described petroleum hydrocarbon is 1-95 % by weight.
8. method according to claim 6, wherein, described petroleum hydrocarbon is petroleum naphtha and/or light hydrocarbon mixture, and described light hydrocarbon mixture is 2-butylene and the C except 2-butylene
1-C
5the mixture of lighter hydrocarbons.
9. method according to claim 8, wherein, in described light hydrocarbon mixture, the content of described 2-butylene is 25-99 % by weight, the C except 2-butylene
1-C
5the total content of lighter hydrocarbons be 1-75 % by weight.
10. method according to claim 1 and 2, wherein, described steam cracking reaction carries out in pyrolyzer, and in described steam cracking reaction process, the coil outlet temperature of described pyrolyzer is 680-839 DEG C, and water weight of oil is than being 0.3-1.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB571736A (en) * | 1942-09-15 | 1945-09-06 | Shell Dev | Dehydrogenation of butenes to butadiene |
| US2873301A (en) * | 1956-04-09 | 1959-02-10 | Sinclair Refining Co | Thermal process for preparing butadiene from butene-2 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB571736A (en) * | 1942-09-15 | 1945-09-06 | Shell Dev | Dehydrogenation of butenes to butadiene |
| US2873301A (en) * | 1956-04-09 | 1959-02-10 | Sinclair Refining Co | Thermal process for preparing butadiene from butene-2 |
Non-Patent Citations (1)
| Title |
|---|
| J.I.ROOS: ""重石油馏分及液化石油气管式炉蒸汽裂解生产烯烃"", 《第十一届世界石油会议报告论文集 第五分册 石油炼制及化工》 * |
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