KR20160132543A - Method for producing conjugated diene - Google Patents
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- KR20160132543A KR20160132543A KR1020150065175A KR20150065175A KR20160132543A KR 20160132543 A KR20160132543 A KR 20160132543A KR 1020150065175 A KR1020150065175 A KR 1020150065175A KR 20150065175 A KR20150065175 A KR 20150065175A KR 20160132543 A KR20160132543 A KR 20160132543A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/11—Purification; Separation; Use of additives by absorption, i.e. purification or separation of gaseous hydrocarbons with the aid of liquids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/12—Alkadienes
- C07C11/16—Alkadienes with four carbon atoms
- C07C11/167—1, 3-Butadiene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
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Abstract
The present invention relates to a method for producing a conjugated diene. According to the present invention, it is possible to reduce the operation pressure of the absorption step or the input amount of the absorption solvent as the absorption treatment condition of the organic solution in which the product gas containing butadiene is absorbed in the organic solvent There is an effect of providing a method for producing a conjugated diene excellent in economical efficiency such as reduction of investment cost or operating cost when the conjugated diene is refined by the introduction of the process.
Description
The present invention relates to a method for producing conjugated diene, and more particularly, to a method for producing conjugated diene, which can reduce the operation pressure of the absorption step or the amount of the absorption solvent supplied as the absorption treatment condition of the organic solution in which the product gas containing butadiene is absorbed in the organic solvent The present invention relates to a method for producing a conjugated diene having excellent economical efficiency such as reduction of investment cost or operation cost when refining the conjugated diene by introducing a process.
1,3-butadiene can be prepared by oxidative dehydrogenation of a monoolefin such as n-butene in the presence of a catalyst.
As prior art for recovering butadiene from the reaction mixture gas containing 1,3-butadiene produced by the oxidative dehydrogenation reaction, U.S. Patent No. 4,595,788 discloses that most of the C4 containing butadiene prior to the crude butadiene separation The components are absorbed by using xylene as the absorption solvent and the residual gas is circulated through the degassing process to the reactor. However, according to these techniques, a process of absorbing the used absorption solvent (xylene) with a higher boiling solvent than xylene was further needed. Therefore, in the purification process of butadiene, economical technology development such as reduction of investment cost or running cost is still required to be.
The object of the present invention is to provide a method for producing a conjugated diene excellent in economical efficiency by introducing a process capable of reducing the operating pressure or the amount of the absorption solvent in the absorption step.
In order to accomplish the above object, the present invention provides a process for producing a n-butene-containing product gas, comprising the steps of: a) preparing a product gas containing butadiene by subjecting a raw material gas containing N-butene to an oxidative dehydrogenation reaction under a catalyst; b) cooling said product gas with water; c) absorbing the cooled product gas into an amide-based organic solvent to produce an absorption solution; And d) degassing and stripping the absorbing solution to obtain crude butadiene, wherein the cooled product gas and the amide organic solvent in step c) and a part of the produced absorbing solution is recycled to the countercurrent flow. The present invention also provides a method for producing a conjugated diene.
According to the present invention, it is possible to reduce the investment cost or the operation cost when refining the conjugated diene by introducing a process capable of reducing the operation pressure of the absorption step or the amount of the absorption solvent, as the absorption treatment condition of the absorption solution in which the product gas containing the butadiene is absorbed into the organic solvent It is possible to provide a method for producing a conjugated diene excellent in economical efficiency.
1 is a process diagram schematically illustrating a process for producing a conjugated diene according to the present invention.
Hereinafter, the present invention will be described in detail.
A method for producing a conjugated diene according to the present invention comprises the steps of: a) preparing a product gas containing butadiene by subjecting a raw material gas containing N-butene to an oxidative dehydrogenation reaction under a catalyst; b) cooling said product gas with water; c) absorbing the cooled product gas into an amide-based organic solvent to produce an absorption solution; And d) degassing and stripping the absorbing solution to obtain crude butadiene, wherein the cooled product gas and the amide organic solvent in step c) and a part of the produced absorption liquid is recycled to the countercurrent flow.
In the absorption step as described above, when the water-cooled product gas and the organic solvent have a countercurrent flow and the bottom stream of the countercurrent flow includes a recycle stream, the operating pressure of the absorption tower itself can be lowered The amount of the necessary amide-based organic solvent to be used can be reduced, and the investment cost or operating cost can be greatly reduced when the conjugated diene is refined.
The countercurrent flow may preferably be formed by sending the water-cooled product gas above the tower below the absorber column and sending the amide organic solvent down the tower above the tower.
Examples of the amide organic solvent used as an absorption solvent in the present invention include at least one selected from the group consisting of dimethylformamide, diethylformamide, and dimethylacetamide, and dimethylformamide is preferably used.
The amide-based organic solvent may be supplied to the upper part of the absorber column at a temperature of 5 ° C to 40 ° C, preferably 5 ° C to 20 ° C, and most preferably 5 ° C to 10 ° C, It has an excellent absorption ability.
The recycle stream may preferably be formed by flowing the absorption liquid discharged from the lower outlet of the absorption tower back to the lower portion of the absorption tower. Here, the lower part of the absorption tower to which the recycle flow is connected may mean one point from the midpoint of the absorption tower to the point where the product gas is introduced.
The absorption in the step c) may be, for example, the weight ratio (DMF / BD) between the feed flow rate of the butadiene and the feed flow rate of the amide organic solvent contained in the cooled product gas is 5 to 6.77 or 5.23 to 6.77, Within this range, there is an effect of excellent absorption ability.
The recycle flow is, for example, one in which the absorption solution flows in a countercurrent flow, that is, in the absorber column of 15 stages or less, preferably 10 stages or less, and most preferably 11 stages or less, It is possible to provide the effect of using the least amount of solvent compared to the reflux rate to be supplied at a point or more.
The recycle flow may be, for example, a mass reflux ratio of 0.5 to 0.7, or 0.55 to 0.65 , And the effect of reducing the operating pressure or the amount of the organic solvent input within this range is excellent.
The absorption in step c) may be carried out, for example, at an upper operating pressure of 12 kg / cm 2 g or less or 7 kg / cm 2 g to 12 kg / cm 2 g of the absorber column, 0 > C to 40 < 0 > C. Particularly, the upper operating pressure of the absorption tower is conventionally a high pressure exceeding 12 kg / cm 2 g, which is reduced by using the above-mentioned counter current flow and recirculating flow in combination, .
The lower operating pressure of the absorber upon the upper operating pressure of the above-described absorber can typically range from, may be 12kg / cm 2 g to about 12.5kg / cm 2 g, for example.
Hereinafter, a method for producing the conjugated diene according to the present invention including the absorption conditions will be described in detail with reference to the accompanying drawings.
1 is a process diagram schematically illustrating a process for preparing butadiene according to the present invention.
First, a step of oxidizing and dehydrophobizing a raw material gas containing N-butene under a catalyst to produce a product gas containing butadiene.
The N-butene is 1-butene, 2-butene or a mixture thereof.
For example, the raw material gas containing N-butene can be obtained by a process comprising the steps of mixing N-butene gas of high purity, oil containing N-butene as a main component obtained by separating butadiene and i-butene from C 4 oil fraction produced as a by- Butene fractions produced by dehydrogenation or oxidative dehydrogenation reaction, reaction product gases obtained by dimerization of ethylene, or hydrocarbons of 4 carbon atoms obtained from fluid catalytic cracking of heavy oil fractions .
The raw material gas containing N-butene may contain at least 40 vol%, preferably at least 60 vol%, more preferably at least 75 vol%, particularly preferably at least 99 vol%, of N-butene, Within this range, the reaction rate and yield are excellent.
The catalyst may be, for example, a molybdate-bismuth-based catalyst.
The molybdate-bismuth-based catalyst is not particularly limited as long as it is a molybdate-bismuth-based catalyst that can be generally used for oxidative dehydrogenation reaction of butene.
The molybdate-bismuth-based catalyst may be, for example, a complex oxide catalyst containing molybdenum, bismuth, and cobalt.
The oxidative dehydrogenation reaction may be, for example, a reaction for producing butadiene by reacting a feed gas containing N-butene and a molecular oxygen-containing gas under a catalyst.
The molecular oxygen-containing gas is, for example, a gas containing 10 to 50 volume%, preferably 15 to 30 volume%, and more preferably 20 to 25 volume% of molecular oxygen.
The molecular oxygen-containing gas may include, for example, impurities such as nitrogen, argon, neon, helium and the like which do not greatly impair the oxidative dehydrogenation reaction.
As another example, the molecular oxygen-containing gas may be air.
For example, in supplying the raw material gas and the molecular oxygen-containing gas to the reactor, the raw material gas and the molecular oxygen-containing gas may be firstly mixed and the mixed gas may be supplied to the reactor. The ratio of the source gas in the mixed gas may be, for example, from 4.2% by volume to 20.0% by volume.
In addition to the mixed gas, for example, nitrogen gas and / or steam can be supplied to the reactor. The introduction of the nitrogen gas has the effect of controlling the concentration of the combustible gas and oxygen so that the mixed gas does not form a detonating gas The introduction of the steam controls the concentration of the combustible gas and the oxygen, and also has an effect of suppressing deterioration of the catalyst.
The reactor used in the oxidative dehydrogenation reaction is not particularly limited as long as it is a conventional reactor used in this technical field, and may be, for example, a tubular reactor, a shaping reactor, a fluidized bed reactor or a fixed bed reactor.
The fixed bed reactor may be, for example, a multi-tubular reactor or a plate reactor.
The fixed-bed reactor includes, for example, a catalyst layer on which the oxidation dehydrogenation catalyst is immobilized. The catalyst bed may be composed of only a catalyst, or may be composed of a solid material that is not reactive with the catalyst, Can be composed of a plurality of or a plurality of layers.
In the case of including the solid or solid containing layer, a rapid temperature rise of the catalyst layer due to heat generation during the reaction can be suppressed. Further, when there are a plurality of catalyst layers, the plurality of layers may be layered from the inlet of the reactor to the direction of the product gas outlet of the reactor.
When the catalyst layer comprises a layer composed of a solid which is not reactive with the catalyst, the dilution rate of the catalyst represented by the following formula may be 10 vol% to 99 vol%, for example.
Dilution ratio = [(volume of solids) / (volume of catalyst + volume of solids)] X 100
The non-reactive solid matter is not limited as long as it is stable under the conditions for producing conjugated dienes, is a raw material such as a monoolefin having 4 or more carbon atoms, and a material that is not reactive with products such as conjugated dienes. A ceramic material such as alumina or zirconia, or the like.
The shape of the non-reactive solid may be spherical, cylindrical, ring, or irregular. Further, the size may be a size equal to the catalyst used in the present description as an example, the particle size may be on the order of 2mm to 10㎜ example.
When the charge length of the catalyst layer is determined as the activity of the catalyst to be charged (in the case of dilution with a non-reactive solid, the activity as a diluted catalyst), the size of the reactor, the reaction material gas temperature, the reaction temperature and the reaction conditions, material balance and heat balance calculations.
The oxidative dehydrogenation reaction is usually an exothermic reaction. For example, the oxidative dehydrogenation reaction is controlled at 250 ° C to 450 ° C, and heat generation can be controlled using a heating medium (for example, dibenzyltoluene or nitrite).
If the reaction temperature, that is, the temperature of the catalyst layer exceeds 450 ° C, the catalytic activity may decrease rapidly as the reaction continues. If the temperature of the catalyst layer is lower than 250 ° C, the yield of the conjugated diene as the target product tends to decrease .
Pressure in the reactor can be at least 0MPaG for example, greater than or 0MPaG 0.5MPaG to within the range, the residence time in the reactor may be 0.36 sec to 72 sec, the ratio of the flow rate of the mixed gas to the catalytic amount in the reactor is to 50h -1 10000h < -1 >.
The flow rate difference between the inlet and the outlet of the reactor depends on the flow rate of the raw material gas at the reactor inlet and the flow rate of the product gas at the reactor outlet but the flow rate of the outlet to the inlet flow rate (100% by volume) To 110% by volume. Thus, the conjugated diene corresponding to the monoolefin is produced by the oxidative dehydrogenation reaction of the monoolefin in the raw material gas, and the produced gas containing the conjugated diene is obtained at the outlet of the reactor. The concentration of the conjugated diene corresponding to the monoolefin in the feed gas contained in the produced gas depends on the concentration of the monoolefin contained in the feed gas, but may be, for example, from 1% by volume to 15% by volume and the unreacted monoolefin May be 0 vol% to 7 vol%.
The high-boiling point by-products contained in the product gas are not limited unless otherwise specified, such as butadiene dimer (BD dimer), 4-formylcyclohexene and 4-acetyl-1-cyclohexene, Lt; / RTI >
The amount of the high boiling point by-products may be, for example, 0.01 to 2% by weight, or 0.1 to 2% by weight in the product gas.
The oxidation dehydrogenation reaction in step a) is, for example, a conversion of 95% or more, or 96% or more. In the above range, unsaturated aldehydes present in the solution before the butadiene separation (acrolein corresponding to the high boiling point by- Tenon, benzaldehyde) is preferable because the content thereof is small.
The product gas comprising butadiene prepared by an oxidative dehydrogenation reaction in an oxidative dehydrogenation reactor (not shown) in FIG. 1 is fed to a quencher as cooling step b) and cooled, and the butadiene-containing The steam, i.e., the cooled product gas, is absorbed into the organic solvent to produce an organic solution, i.e., an absorption solution.
In the cooling tower, cooling water is introduced upward by piping and countercurrently contacted with the product gas introduced into the lower portion. The cooling water that has cooled the product gas by the countercurrent contact is discharged to the piping of the column bottom. At this time, some or all of the discharged cooling water may be cooled in the heat exchanger and circulated again in the cooling tower.
Specifically, the cooling is performed by spraying water at a temperature of 30 ° C to 50 ° C, or 35 ° C to 45 ° C, on the top of the cooling tower, and condensing the lower drainage water by cooling and recycling a part of the recirculated water, Is injected into the aldehyde removing column, and water at 10 to 30 DEG C, or 15 to 25 DEG C is injected into the upper part of the removal column, and the lower drainage water is allowed to stand for 1 hour or less, or for 40 minutes to 1 hour under reduced pressure heating condition, And then recycled to the removal tower.
The reduced pressure heating condition may be, for example, a condition of 30 mbar / (30 to 60 ° C) to 150 mbar / (30 to 60 ° C), or a condition of 50 mbar / (40 to 55 ° C) (40 DEG C to 55 DEG C).
The cooled product gas flows out to the top of the cooling tower, is then raised to a predetermined pressure through the compressor, and then supplied to the absorber as the step c) to make countercurrent contact with the amide organic solvent as the absorption solvent. The amide organic solvent may be at least one selected from the group consisting of dimethylformamide, diethylformamide and dimethylacetamide, preferably dimethylformamide, and may be used in an amount of 5 Lt; 0 > C to 40 < 0 > C.
The weight ratio (DMF / BD) between the feed flow rate of the butadiene and the feed flow rate of the amide organic solvent contained in the butadiene-containing steam supplied to the absorption tower in the step c) 6.77.
Due to the countercurrent contact, butadiene in the product gas, unreacted raw material gas and the like are absorbed in an organic solvent such as dimethylformamide. Here, the gas components not absorbed in dimethylformamide can be discharged to the top of the absorber and burned off or sent back to the reactor to be circulated.
The product gas absorption liquid containing the unreacted raw material gas of butadiene is discharged to the bottom of the absorption tower and supplied to the upper part of the degasser through the piping.
As a specific example, the recycle stream may be introduced into the absorption column in the 10th to 12th stages of the theoretical stages among the 15 stages of the absorber column, and may be introduced into the 11th stage as the most preferable example.
As an example, the recycle flow may preferably have a mass reflux ratio in the range of 0.55 to 0.65.
Wherein c) the absorption step in an example, the absorber (upper operating pressure 7kg / cm 2 g to 12kg / cm 2 g, the lower operating pressure 12kg / cm 2 g to about 12.5kg / cm 2 g, and absorption of the absorber column) The treatment can be carried out at a temperature of 0 ° C to 50 ° C, and oxygen or nitrogen or the like is not easily absorbed in the solvent within the above range, and absorption efficiency of hydrocarbons such as conjugated dienes can be good.
The organic gas absorption liquid prepared in the step c) may be subjected to a degassing process by spraying the organic solution onto the upper part of the degassing tower at a feed temperature of 30 ° C to 40 ° C before the stripping process, In this case, there is an effect of removing nitrogen or oxygen dissolved in the absorbing solution.
Since a small amount of nitrogen and oxygen are also dissolved in the product gas absorption liquid obtained in the absorption tower, the product gas absorption liquid is supplied to the deaeration tower as a first step of d) and heated to be gasified and removed. At this time, since the butadiene or a part of the source gas may be gasified, the gas discharged to the top of the deaerator tower is circulated to the inlet side of the compressor in order to increase the recovery rate of butadiene.
In the degassing step, the degassing treatment may be carried out under a temperature condition of 110 ° C to 130 ° C, and the degassed product gas absorbing solution is supplied through a pipe to the solvent separating tower (Stripper) as the second step of d). In the solvent separation column, a product gas absorption liquid containing a reboiler (lower portion) and a condenser (upper portion) is distilled off, crude butadiene is extracted from the column, and the separated dimethylformamide is discharged to the column bottom. At this time, the dimethylformamide discharged from the bottom can be circulated through the absorption solvent.
If necessary, the condensed water may be separated and discharged from the generated gas by passing the generated gas discharged from the top of the quencher to the compressor before passing the condensed gas through the cooler. Further, the dehydration process can be performed by passing the product gas that has risen after passing through the compressor through a dehydration tower filled with a drying material such as a molecular sieve before passing the product gas into the absorption tower.
The stripping is not particularly limited as long as it is a stripping method capable of separating the crude butadiene from the solvent.
For example, the stripping can be effected by distillation separation.
The distillation separation may be, for example, a method of distilling a product gas absorption liquid by a reboiler and a condenser to extract crude butadiene from the column top.
For example, the organic solution from which residual gas has been removed by the deaeration treatment may be cooled to a temperature of 10 ° C to 30 ° C and then sprayed onto the top of the solvent separation column. The remaining crude stripped butadiene solution can be re-used as an organic solvent in the second stage of b).
For example, the crude butadiene in step d) may have a purity of 1.3 to 99% by weight or 95 to 98% by weight of 1,3-butadiene, 0.1 to 2% by weight of the high boiling point by- 0.1% by weight to 1% by weight.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope and spirit of the invention as disclosed in the accompanying claims. Changes and modifications may fall within the scope of the appended claims.
[Example]
The cooling tower used in this embodiment was designed to have a filling column of 3 m in height, a water inlet at the top, waste water discharge at the lower end, and a reflux (condenser). The absorption tower uses a filling column having a height of 7 m (DMF) at the top and re-boiler and reflux (condenser) at the bottom for the purpose of extractive distillation.
Example One
First, a multicomponent bismuth molybdenum catalyst (Mo 1-15, Bi 1-10, Fe 1-10, Co 1-10, K 0.01-1.5, and a complex oxide catalyst having a composition ratio of Cs 0-1.5) The reactor was filled with a tubular reactor and subjected to an oxidative dehydrogenation reaction at 320 ° C. while supplying a raw material gas at a space velocity of 75 h -1 , oxygen / 1-butene = 1, steam / 1-butene = 3 and nitrogen / Butadiene was produced (conversion rate: 98%).
The product gas was cooled by spraying 9 kg / h of water at 40 DEG C in the upper part of the cooling tower, and 0.4 kg / h was discharged from the lower part of the cooling tower as wastewater containing high boiling point by-products and then discharged from the top of the quencher The gas was compressed with a compressor (pneumatic gas booster) and then fed to the absorber. At this time, the temperature of the gas was 30 ° C to 35 ° C, and the flow rate of the product gas introduced into the absorption tower was 49,705 kg / h.
Dimethylformamide (DMF) was sprayed onto the top of the absorber at a rate of 47.786 kg / h, which was 5.23 times the weight of the feed stream of butadiene in the product gas entering the absorber.
The stream of the absorption liquid containing unreacted product gas in the lower outlet of the absorption tower was then refluxed to the bottom of the absorption tower (theoretical stage 11) under the recirculating flow conditions to form a stream of recycle.
At this time, the composition of the gas discharged without being absorbed to the upper part of the absorption tower and the composition of the conjugated diene-containing absorption solution discharged to the lower part were measured by gas chromatography (Agilent Technologies 5890N, colum: HP-1 (FID) with PORAPAK-Q / 5A (TCD), and then held 0 ℃ to 22 minutes to 32 minutes the temperature was raised to 100 ℃, after 3 minutes the temperature holding that after by up to 51 minutes the temperature was raised to 260 ℃ analysis 71 minutes ended, wherein the temperature raising rate is 10 ℃ · min - 1 ), and the absorptivity (absorption amount / inflow amount) of the detection components including butadiene calculated therefrom is shown in Table 1 below.
<Absorption conditions and recirculation Flow condition >
Gas inlet (kg / h): 49,705
Solvent inlet (kg / h): 47,786
Reflux rate (kg / h): 100,007
Reflux temperature (° C): 5.0
Reflux stage (#): 11
Column Top P (kg / cm 2 g): 12.0
Top rate (kg / h): 36979.52
Absorbed rate (kg / h): 64010.83
Reflux flow / Bottom flow: 0.610 (Bottom flow corresponds to total bottom flow before reflux)
Example 2
The same procedure as in Example 1 was repeated except that the absorption condition and the recycle flow condition were changed as follows in Example 1, and the absorption ratios of the detection components including butadiene, calculated therefrom, Respectively.
<Absorption conditions and recirculation Flow condition >
Gas inlet (kg / h): 49,705
Solvent inlet (kg / h): 61,929
Reflux rate (kg / h): 100,001
Reflux temperature (° C): 5.0
Reflux stage (#): 11
Column Top P (kg / cm 2 g): 8.5
Top rate (kg / h): 37136.17
Absorbed rate (kg / h): 77939.08
Reflux / Bottom: 0.562
Comparative Example One
The same procedure as in Example 1 was repeated except that the absorption condition and the recycle flow condition were changed as follows in Example 1, and the absorption ratios of the detection components including butadiene, calculated therefrom, Respectively.
<Absorption conditions and recirculation Flow condition >
Gas inlet (kg / h): 49,705
Solvent inlet (kg / h): 62,476
Reflux rate (kg / h): -
Reflux temperature (℃): -
Reflux stage (#): -
Column Top P (kg / cm 2 g): 12.0
[Table 1]
As shown in Table 1, when the countercurrent flow and the recycle flow are used together, the amount of the organic solvent is reduced as demonstrated in Example 1 while maintaining the high butadiene absorption rate of 99.5%, or 99.5% It was confirmed that the operation pressure could be reduced in the absorption step as demonstrated in Example 2 while maintaining the butadiene absorption rate of%.
On the other hand, in the case where the countercurrent flow is used according to the prior art but the flow of the recycle is not used in combination, as shown in Comparative Example 1, in order to maintain the 99.5% butadiene absorption rate as in Examples 1 and 2, It was confirmed that the pressure could not be increased.
Claims (9)
Characterized in that the cooled product gas and the amidic organic solvent in step c) have a counterflow and a part of the produced absorption solution is recycled to the countercurrent flow
Gt;
Wherein the countercurrent flow is formed by passing the cooled product gas below the absorber column on top of the column and sending the amide organic solvent down the column above the column
Gt;
Wherein the amide organic solvent is at least one selected from the group consisting of dimethylformamide, diethylformamide, and dimethylacetamide
Gt;
Wherein the amide organic solvent is supplied to the upper part of the absorber column at a temperature of 5 ° C to 40 ° C
Gt;
Wherein the recycle stream is formed by circulating the produced absorption solution back to the bottom of the absorption tower.
Wherein the absorption of step (c) is performed such that the weight ratio (DMF / BD) between the feed flow rate of the butadiene and the feed flow rate of the amide organic solvent contained in the cooled product gas is 5 to 6.77.
The recycle stream is characterized in that the absorption solution is introduced into the absorber column of 15 stages or less at the theoretical stage of 8 stages or less
Gt;
Characterized in that the absorption of step c) is carried out at an upper operating pressure of the absorber column of 7 kg / cm 2 g to 12 kg / cm 2 g and at an absorption treatment temperature of 0 ° C to 50 ° C
Gt;
Wherein the catalyst of step a) is a molybdate-bismuth-based catalyst.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120026049A (en) * | 2009-05-29 | 2012-03-16 | 미쓰비시 가가꾸 가부시키가이샤 | Method for producing conjugated diene |
| JP2012072086A (en) * | 2010-09-29 | 2012-04-12 | Asahi Kasei Chemicals Corp | Method of producing butadiene |
| JP2012082153A (en) * | 2010-10-08 | 2012-04-26 | Asahi Kasei Chemicals Corp | Process for producing butadiene |
| JP2012106942A (en) * | 2010-11-16 | 2012-06-07 | Mitsubishi Chemicals Corp | Method for producing conjugated diene |
| CN103086829A (en) * | 2013-01-30 | 2013-05-08 | 中国石油化工股份有限公司 | Recycling method for butylene oxidative dehydrogenation wastewater |
| WO2014148323A1 (en) * | 2013-03-18 | 2014-09-25 | Jsr株式会社 | 1,3-butadiene production method |
| KR20140132806A (en) * | 2013-05-06 | 2014-11-19 | 주식회사 엘지화학 | Manufacturing method of conjugated diene compound |
-
2015
- 2015-05-11 KR KR1020150065175A patent/KR102008794B1/en active IP Right Grant
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120026049A (en) * | 2009-05-29 | 2012-03-16 | 미쓰비시 가가꾸 가부시키가이샤 | Method for producing conjugated diene |
| JP2012072086A (en) * | 2010-09-29 | 2012-04-12 | Asahi Kasei Chemicals Corp | Method of producing butadiene |
| JP2012082153A (en) * | 2010-10-08 | 2012-04-26 | Asahi Kasei Chemicals Corp | Process for producing butadiene |
| JP5717393B2 (en) * | 2010-10-08 | 2015-05-13 | 旭化成ケミカルズ株式会社 | Butadiene manufacturing process |
| JP2012106942A (en) * | 2010-11-16 | 2012-06-07 | Mitsubishi Chemicals Corp | Method for producing conjugated diene |
| CN103086829A (en) * | 2013-01-30 | 2013-05-08 | 中国石油化工股份有限公司 | Recycling method for butylene oxidative dehydrogenation wastewater |
| WO2014148323A1 (en) * | 2013-03-18 | 2014-09-25 | Jsr株式会社 | 1,3-butadiene production method |
| KR20140132806A (en) * | 2013-05-06 | 2014-11-19 | 주식회사 엘지화학 | Manufacturing method of conjugated diene compound |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190098694A (en) * | 2018-02-14 | 2019-08-22 | 주식회사 엘지화학 | Method for filling catalyst and method for preparing butadiene using same |
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