KR20180077736A - Method for producing conjugated diene - Google Patents

Abstract

The present invention relates to a method for producing butadiene and a production apparatus. More specifically, provided are a method for producing butadiene and a production apparatus. According to the present invention, by using butane as diluent gas, gas products and a C4 mixture other than butadiene can be easily separated even if a refrigerant lower than a cryogenic refrigerant is used, thereby securing high purity butane and economic feasibility in a process in addition to improvement in productivity and reduction in production costs and energy.

Description

[0001] METHOD FOR PRODUCING CONJUGATED DIENE [0002]

The present invention relates to a process for producing butadiene, and more particularly, to a process for producing butadiene, which is capable of securing high purity butadiene, such as reduction of energy and raw material costs, improvement of productivity, and the like.

Butadiene is used as an intermediary for many petrochemical products in the petrochemical market. It is one of the most important basic oil in the petrochemical market and its demand and value are gradually increasing.

Butadiene can be produced by extraction from C4 oil through naphtha cracking, direct dehydrogenation of butene, and oxidative dehydrogenation of butene.

The method of preparing butadiene through the oxidative dehydrogenation reaction of butenes uses the reaction of removing two hydrogen from butene by using oxygen as a reactant to produce butadiene. Since the product is stable water, it is thermodynamically And it is an exothermic reaction unlike the direct dehydrogenation reaction, so that a higher yield of butadiene can be obtained even at a lower reaction temperature than the direct dehydrogenation reaction. Thus, the production of butadiene by oxidative dehydrogenation of butene can be an effective production process to meet the increasing demand for butadiene.

Meanwhile, in the oxidative dehydrogenation process of butene, nitrogen, steam and the like are used as a diluting gas in addition to raw materials in order to reduce the risk of explosion due to oxygen and to remove reaction heat. However, dilution gas and light A method of absorbing hydrocarbons in a reaction product by using a solvent to separate hydrocarbons from a reaction product containing gas streams (COx, O _2, etc.), hydrocarbons, etc., and a method of liquefying hydrocarbons by cooling a reaction product The absorption method is mainly used. This is because the method of liquefying and separating the reaction product requires a cryogenic refrigerant when liquefied due to a dilution gas present in the reaction product and a light gas stream or the like, which makes it difficult to secure the economical efficiency of the process due to an increase in equipment cost and operating cost Because

In this regard, FIG. 1 is a view for explaining a conventional butadiene producing apparatus and method.

1, a reaction raw material containing butene, oxygen (O ₂ ), steam, and diluent gas (N ₂ ) is passed through an oxidative dehydrogenation reaction unit 110 to produce butadiene obtained from an oxidative dehydrogenation reaction A cooling separator 120 for separating water from the C4 mixture and the gaseous product; An absorption separator 130 separating the C4 mixture and the hydrocarbons including butadiene or butadiene from the oxidation dehydrogenation reaction product in which the water is separated; And a purifier 140 for separating butadiene from a stream containing butadiene separated from the absorption separator 130. The absorption separator 130 may be configured to selectively adsorb hydrocarbons use of the solvent the COx, O _2, part of n- butane and select the hydrocarbon other than the N ₂ is used as a diluent gas absorption, or which may be full absorption.

The oxidative dehydrogenation reaction unit 110 may include a gas containing butene, oxygen (O ₂ ), steam, a diluent gas (N ₂ ), and unreacted butenes recovered in the purification unit, Or may be driven under isothermal or adiabatic conditions using a catalyst or a bismuth molybdate-based catalyst.

The cooling separator 120 may be driven by a quencher or an indirect cooling system.

1, only the butadiene is selectively absorbed and separated in the absorption separator 130. The absorption separator 130 selectively absorbs only butadiene in the reaction product from which the water is removed, or the entire hydrocarbons including the C4 mixture It may be driven by an absorption method using an absorbable solvent. The selective absorption solvent may be at least one selected from the group consisting of ACN (Acetonitrile), NMP (N-methylpyrrolidone), and DMF (Dimethyl formamide). As the total absorption solvent, for example, toluene, xylene or a mixture thereof may be used.

The COx, O ₂ , and N ₂ used as the diluent gas separated from the absorption separator 130 are entirely incinerated or partially recycled to the reaction part in some cases, and partially re-used and partially incinerated.

The purifier 140 may be an ordinary butadiene purifier, for example, an ACN (Acetonitrile) process, a NMP (N-methylpyrrolidone) process, a DMF (Dimethylformamide) process, Butadiene can be purified.

However, in order to absorb hydrocarbons from a hydrocarbon mixture containing N ₂ , which is a diluent gas in general, and a gas stream such as CO x and O ₂ , the hydrocarbon is generally required to have a low partial pressure, A large amount of energy is used in the process of recovering and recovering butadiene from the purifier 140. Also, even if the absorption separation process is replaced with a condensation process, a cryogenic refrigerant is required and economical efficiency of the process such as raw material cost and productivity can not be secured.

Korea Patent Publication No. 2012-0103759

In order to solve the problems of the prior art as described above, the present invention relates to an absorption method used for separating butadiene from reaction products during the use of conventional nitrogen using butane instead of nitrogen as a diluent gas in the production of butadiene through oxidative dehydrogenation of butene Instead, a condensation method is used in which the butadiene is liquefied and separated using low temperature refrigerant or cooling water. In order to minimize the loss of the desired product (referred to as butadiene) to be discharged together with the effluent stream containing COx, O ₂ , n-butane and the like separated in the condensation process, the active ingredient (including all butadiene) (Hereinafter referred to as " hydrocarbons "), which is capable of reducing the energy and raw material costs and improving the productivity, and securing the economical efficiency of the process.

These and other objects of the present invention can be achieved by the present invention described below.

In order to achieve the above object,

Passing a reaction raw material including butene, oxygen (O ₂ ), steam and diluent gas through an oxidative dehydrogenation reaction unit to produce an oxidative dehydrogenation reaction product comprising butadiene,

Separating the water while passing the oxidative dehydrogenation reaction product containing the butadiene through the cooling separator,

Condensing the hydrocarbons while passing the oxidative dehydrogenation reaction product in which the water is separated to the condensation separation unit,

Separating COx and O ₂ while passing the oxidative dehydrogenation reaction product containing hydrocarbons not condensed in the condensation separator to the absorption separator,

The crude hydrocarbons containing n-butane, butene and butadiene condensed in the condensing and separating section are separated from the butadiene while being passed through the purification section, or passed through the deaeration section to further separate COx and O _2. Then, n-butane and butene And separating the butadiene while passing the crude hydrocarbon containing the butadiene through the purification section,

The n-butane-containing gas except the butadiene separated in the purifying section is re-introduced into the oxidative dehydrogenation reaction section,

Wherein the butadiene is separated from the refining part and the remaining butane-containing discharge stream is mixed with the raw butene and introduced into the oxidative dehydrogenation reaction part, wherein the diluent gas is butane.

The present invention also provides an oxidative dehydrogenation reaction unit for obtaining an oxidative dehydrogenation reaction product comprising butadiene by oxidative dehydrogenation of a reaction raw material containing butene, oxygen (O ₂ ), steam and diluent gas;

A cooling separator for separating water from the oxidative dehydrogenation reaction product comprising butadiene obtained from the oxidative dehydrogenation reaction;

A condensation separator for condensing hydrocarbons from the oxidized dehydrogenation reaction product in which the water is separated;

An absorption separator for separating COx and O ₂ from the oxidative dehydrogenation reaction product containing hydrocarbons not condensed in the condensation separation unit; And

And a purifier for separating butadiene from crude hydrocarbons containing n-butane, butene and butadiene condensed in the condensation separator,

The n-butane-containing gas except the butadiene separated in the purifying section is re-introduced into the oxidative dehydrogenation reaction section,

Wherein the butadiene is separated from the refining part and the remaining butane-containing discharge stream is mixed with fresh butene, and the diluted gas is introduced into the oxidative dehydrogenation reaction part, wherein the diluent gas is butane.

According to the present invention, instead of nitrogen, butane is used to prepare butadiene through oxidative dehydrogenation reaction of butene, butadiene is liquefied using a low-temperature refrigerant or cooling water instead of the absorption method used for separating butadiene from the reaction product during the conventional nitrogen use (Butadiene) from the hydrocarbons flowing out to the upper stream after the condensation separation, and the absorption separation method of recovering the objective product (butadiene) by minimizing the loss of butadiene, thereby reducing the raw material cost, energy and production cost And to provide a method for producing butadiene which can secure the economical efficiency and high purity of butadiene.

1 is a view for explaining a conventional butadiene producing apparatus and method.
2 to 6 are diagrams for explaining an apparatus for producing butadiene and a method for producing the same according to the present invention.

Hereinafter, the butadiene production method and the production apparatus of the present invention will be described in detail. The butadiene producing method and the apparatus of the present invention are characterized in that a condensation separation process using butane as a diluent gas and an absorption separation process for selectively absorbing and recovering hydrocarbons in a discharge stream flowing out to the outside through an upper part of a condensation separation process are applied to be. If the butane is used as a diluting gas, the condensation separation unit can easily separate the hydrocarbons from the oxidative dehydrogenation reaction product by using a low-temperature refrigerant or cooling water, and select the desired product from hydrocarbons flowing out to the absorption separation unit By recovering by absorption, butadiene that flows out of the system is minimized, butadiene can be economically produced.

Hereinafter, the method and apparatus for producing butadiene of the present invention will be described in detail with reference to the drawings. 2 to 6 are views for explaining an apparatus and a method for producing butadiene according to the present invention.

Referring to FIG. 2, first, a reaction raw material containing butene, oxygen (O ₂ ), steam and diluted gas (butane) is passed through the oxidative dehydrogenation reaction unit 210 to produce butadiene as an oxidative dehydrogenation reaction product And flows into the cooling separator 220 along the flow B1 discharged in the process. At this time, the starting material of the reaction joins with the discharge stream (B7) containing n-butane generated after the purification treatment in the purification process, flows into the oxidation dehydrogenation reaction unit 210, Another discharge stream (B8) including the reaction unit flows into the oxidative dehydrogenation reaction unit 210 by joining with the raw butene. The flow B1 discharged in the oxidative dehydrogenation process may include butadiene, n-butane, butene, O ₂ , CO ₂ , H ₂ O and the like, and flows into the cooling separator 220 to separate water.

Butane, butene, O ₂ , CO ₂ and the like may be included in the discharge flow B2 generated after the cooling and separation, and the condensed water is flowed into the condensation separator 230.

The discharged stream B3 generated after the condensation separation includes the oxidation dehydrogenation reaction product containing condensed hydrocarbons after condensing the hydrocarbons by compression / cooling using cooling water or low temperature refrigerant in the condensation separation process And the other discharge stream B4 generated after the condensation separation may include a crude hydrocarbon containing n-butane, butene and butadiene condensed in the condensation separator 230, Butadiene can be purified.

Generated in the absorption separation process draw stream (B5), the may comprise a separate condensing separating portion (230) O _2, COx and so on, the absorption separation another draw stream (B6) caused by the absorption separation process And a hydrocarbon including n-butane, butene, and butadiene except for COx and O ₂ in the unit 250 may be selectively absorbed in a solvent. The discharge stream B 6 may include a condensate separation unit 230 Can be reintroduced.

The discharged stream (B4) generated after the condensation separation may be passed through the purifier 240 to separate the butadiene. The discharged stream (B7) generated after the purification may abundantly contain residual n-butane, A diluting gas can be supplied to the oxidizing and dehydrogenating unit 210 to form a recirculation flow to concentrate the diluted gas to a required amount, and the butadiene is separated from the purifying unit 240 and the butane- ) May be mixed with raw butene and introduced into the oxidative dehydrogenation reaction unit 210. In this case, the reaction can be continuously performed and the productivity is improved.

The term " crude hydrocarbons " means crude hydrocarbons commonly used in this technical field. Unless otherwise specified, hydrocarbons including butadiene and the like obtained from oxidative dehydrogenation reaction products, Quot;

The term " CO x "refers to CO, CO ₂ unless otherwise specified.

The butene may be 1-butene, 2-butene or a mixture thereof. The raw material gas containing butene is not particularly limited in the case of raw material gas containing butene which can be generally used for the production of butadiene.

For example, the butene can be obtained from a hydrocarbon mixture containing butenes, such as butene gas of high purity, raffinate-2, raffinate-3, and the like among the C4 oils produced by naphtha cracking.

The steam is a gas which is injected for the purpose of preventing the coking of the catalyst and eliminating the reaction heat while reducing the risk of explosion of the reactant in the oxidative dehydrogenation reaction.

On the other hand, the oxygen (O ₂ ) reacts with butene as an oxidizing agent to cause a dehydrogenation reaction.

The catalyst packed in the reactor is not particularly limited as long as it enables the production of butadiene by oxidative dehydrogenation reaction of butene, and may be, for example, a ferrite catalyst, a bismuth molybdate catalyst or an iron catalyst.

In one embodiment of the present invention, the catalyst may be a ferrite-based catalyst. Among them, use of zinc ferrite, magnesium ferrite, and manganese ferrite may enhance the selectivity of butadiene. The type and amount of the reaction catalyst may vary depending on the specific conditions of the reaction.

The diluent gas may be butane.

The oxidation dehydrogenation reaction unit 210 may include butane, oxygen (O ₂ ), steam, and butadiene in the purification unit 240 as residues separated from the oxidation dehydrogenation reaction unit But may be one which is driven under an isothermal or adiabatic condition using a gas containing n-butane as a feedstock and a ferritic catalyst or an iron catalyst.

For example, oxygen (O ₂ ) contained in the reaction raw material may be introduced in a gas having a purity of 90% or more, 95% or more, or 98% or more.

The gas form having a purity of 90% or more may mean that oxygen (O ₂ ) is not introduced from the air but is introduced in the form of pure oxygen gas. Thus, the amount of the active ingredient, So that the amount of the components contained in the reaction starting material fed into the reactor can be individually controlled, and most of the supplied oxygen can be burned off.

For example, the reaction conditions in the oxidative dehydrogenation reaction unit 210 may be a molar ratio of butene: oxygen: water vapor: diluent gas (n-butane) = 1: 0.5~3: 0.05~20: 0.05~20.

As a specific example, the oxidative dehydrogenation reaction unit 210 may have an oxygen dehydrogenation reaction unit 210 in which the mole ratio of oxygen to butene is 0.5 to 3: 1, the mole ratio of steam to butene is 0.05 to 20: 1, the mole ratio of n-butane: butene is 0.05 to 20: To 10 atm, and a reaction temperature of 150 to 650 ° C.

For example, the cooling separator 220 may be driven by a quencher or an indirect cooling system. In this case, the quenching temperature is a temperature at which water is cooled while the hydrocarbons are not cooled, For example, from 0 to 100 < 0 > C.

For example, the condensation separator 230 may have a single compression structure of one stage, a multi-stage compression structure of two to ten stages, or a multi-stage compression structure of one or two stages. The reason for performing the above-described multi-step compression is that, when compressed from the initial pressure to the target pressure at one time, not only a lot of power is required but also heat due to gas compression is generated and the gas expands and the compression efficiency is lowered. So that the heat generated in the compression process can be cooled using a cooler.

The condensation condition in the condensation separator 230 may be determined to have a range in which the flow is out of the explosion range (above the explosion upper limit or below the critical oxygen concentration) in consideration of unreacted oxygen.

In an embodiment of the present invention, the refrigerant used in the condensing and separating unit 230 may include cooling water, ethylene glycol, an ethylene glycol aqueous solution having a concentration of 20 to 100% by weight, propylene glycol, a propylene glycol aqueous solution having a concentration of 30 to 100% And a propylene-based solvent. The propylene-based solvent is, for example, a compound containing propylene or propylene, and may be a substance having a boiling point of -10 ° C or less or -10 to -50 ° C.

The refrigerant may be chilled water, cooling water at 0 to 40 ° C or cooling water at 5 to 30 ° C. In this case, the extrusion discharge temperature may be 250 ° C or less, or 50 to 200 ° C. The cooling temperature may be 120 占 폚 or lower, or 20 to 80 占 폚.

Conventionally, when nitrogen is used as a diluting gas and a diluting gas and a light gas stream are separated by a condensing method, it is required to use a cryogenic refrigerant. In the present invention, however, by introducing butane into a diluting gas, It became possible.

The purification unit 240 may be a conventional apparatus for purifying butadiene. For example, the purification unit 240 may be an ACN (Acetonitrile) process, an NMP (N-methylpyrrolidone) process, or a DMF (Dimethylformamide) process. The solvent used in the purification unit 240 may be the same as the solvent used in the absorption and separation unit 250, or other solvent may be used if necessary. The solvent may be separated from the purifying part 240 and circulated to the absorption separating part 250 (not shown in the discharge flow).

The absorbing and separating unit 250 may be an absorbing method using a solvent such as ACN (Acetonitrile), NMP (N-methylpyrrolidone), or DMF (Dimethyl formamide) capable of selectively absorbing butadiene, butene and the like among hydrocarbons. Lt; / RTI > When the COx and O ₂ separated from the absorption separator 250 are incinerated, heat generated by the incineration can be recycled in the oxidation dehydrogenation reactor 210 or the condensation separator 230.

The butadiene obtained through the separation step can be recovered as highly pure butadiene by removing the solvent, high boiling point and low boiling point components through a purification step.

In one embodiment of the present invention, the purity of finally obtained butadiene through the series of steps may be 95.0 to 99.9%.

FIG. 3 is a graph showing the results of the oxidation dehydrogenation reaction product in which water is separated from the cooling separator 220 in FIG. 2 through the condensing separator 230 and the absorption separator 250, ), Including deaeration and solvent recovery.

The deaeration section may be driven by stripping using a conventional column, or degassing.

Referring to FIG. 3, first, a reaction raw material containing butene, oxygen (O ₂ ), steam, and diluted gas (butane) is passed through an oxidative dehydrogenation reaction unit 310, Generates a reaction product, and flows into the cooling separator 320 along the flow B1 discharged in the reaction process. At this time, the reaction raw material is purified by the purification process, and the n-butane-containing gas generated after the purification is introduced into the oxidation dehydrogenation reaction unit 310 along the discharge flow B7, The reaction unit flows into the oxidative dehydrogenation reaction unit 310 by joining with the raw butene along the discharge flow B8.

The stream B 1 discharged from the reaction process may include butadiene, n-butane, butene, O ₂ , CO ₂ , H ₂ O, etc., and flows into the cooling separator 320 to separate water.

The exhaust stream B2 generated after the cooling and separation may include butadiene, n-butane, butene, O ₂ , CO ₂ , and the like, and flows into the condensation separator 330.

The discharged stream B3 generated after the condensation separation includes the oxidation dehydrogenation reaction product containing condensed hydrocarbons after condensing the hydrocarbons by compression / cooling using cooling water or low temperature refrigerant in the condensation separation process . Another effluent stream B4 'generated after the condensation separation may include condensed n-butane, hydrocarbons including butene and butadiene.

A discharge flow (B11) occurs after the stripping can be separated absorbed by introducing further said absorption separation unit 350 includes a COx and O _2, and separated in the degassing unit 360, the after the degassing occurs another draw stream (B4 ") may be purified by the butadiene fed to the degassing unit 360 added COx and O ₂ can be a crude hydrocarbon and the purified 340 except separated from.

Said generated in the absorption separation process draw stream (B5), the discharge flow (B3) containing the O _2, COx and so on away from the condensate separation unit 330, and the O _2, COx and so on away from the degassing unit 360 including removal by selective absorption of hydrocarbons such as the emission flow (B11), with butadiene or part Tenryu and remaining O _2, it may include COx and so on, another draw stream generated after the absorption separation (B6 ') has In the absorption separator 350, crude hydrocarbons including n-butane, butene, and butadiene except for COx and O ₂ may be absorbed in the solvent.

The exhaust stream B7 generated after the butadiene separation and purification passes through the purifier 340 may be abundant in the remaining n-butane and forms a recycle stream to be fed into the oxidation dehydrogenation reactor 310 do.

The solvent in the refining unit 340 can be separated and circulated to the absorption separator 350 (the discharge stream B9), and the discharge stream B8 in which the butadiene and the solvent are separated and the residual butene is contained, Butene and the like to be mixed with butene, and then introduced into the oxidative dehydrogenation reaction part 310, because the reaction can proceed continuously.

FIG. 4 shows another addition of the discharge flow B4 '' to the discharge flow B4 '' generated after the degassing in FIG. 3, wherein the discharge flow B4 ' The crude hydrocarbons may be included except for COx and O ₂ , and the high boiling point component is separated from the crude hydrocarbons while passing through the high boiling point rejection 470, and the high boiling point material (B 4 ''' And the crude hydrocarbons can purify the butadiene more efficiently in the purifying section 440. [

The high boiling point remover may be driven by a conventional distillation column method or the like.

The high-boiling substance may be, for example, furan, aldehydes, aromatic hydrocarbons such as acetic acid, benzene, phenol, or styrene.

4, first, a reaction raw material including butene, oxygen (O ₂ ), steam, and diluent gas (butane) is passed through an oxidative dehydrogenation reaction unit 410 to perform oxidation dehydrogenation reaction including butadiene And flows into the cooling separator 420 along the flow B1 discharged in the reaction process. At this time, the raw material of the reaction is refined in the purification process, and then the n-butane used as the diluting gas flows into the oxidation dehydrogenation reaction part 410 along the discharge flow B7, and after the purification treatment, (B8) and flows into the oxidative dehydrogenation reaction unit (410).

The stream B 1 discharged from the oxidative dehydrogenation reaction may include butadiene, n-butane, butene, O ₂ , CO ₂ , H ₂ O and the like, and flows into the cooling separator 420 to separate water.

Butane, butene, O ₂ , CO ₂ and the like may be included in the discharge flow B2 generated after the cooling and separation, and the condensed water is flowed into the condensation separation unit 430.

The discharged stream B3 generated after the condensation separation includes the oxidation dehydrogenation reaction product containing condensed hydrocarbons after condensing the hydrocarbons by compression / cooling using cooling water or low temperature refrigerant in the condensation separation process And another effluent stream B4 'generated after the condensation separation may include hydrocarbons including condensed n-butane, butene and butadiene.

A discharge flow (B11) occurs after the degassing has the hydrocarbons charged into a degassing 460 added may include COx and O _2, the absorption separation section 450 separated from be separated absorption. Another draw stream (B4 ") after the above degassing occurs may be an n- butane, butene and butadiene crude hydrocarbon includes, except for the COx and O ₂ separated by additional degassing at 460, the high-boiling jeomje rejected ( 470) to separate high boiling point components from the crude hydrocarbons, and the exhaust stream (B4 ''') generated in the high boiling point removal process may contain crude hydrocarbons having high boiling point components removed and containing butadiene, The butadiene can be purified by passing the discharge stream B4 "'containing the hydrocarbon to the purification section 440. [

As in Figure 3, O ₂ in the exhaust stream (B3) and, de-base 460 is, including the separation in the condensate separation unit (430) O _2, COx such as a discharge flow (B5) generated in the absorption separation process , may be included in the discharge flow (B11) including COx and so on, selected absorbent to remove hydrocarbons such as butadiene or a portion included Tenryu and remaining O _2, such as COx. Crude hydrocarbons including the generated separation after absorption Another draw stream (B6 ') include n- butane, except for COx and O ₂ on the absorption separation unit 450, such as butenes and butadiene The include those that are absorbed in the solvent, And is introduced into the deaeration section 460.

The discharged stream B7 generated after the butadiene separation and purification after passing through the purifying section 440 may be abundantly contained in the remaining n-butane to form a recycle stream to be fed into the oxidative dehydrogenation reaction section 410 do. The solvent can be separated from the purifying section 440 and circulated to the absorption separating section 450 (the discharge flow B9), and the discharge flow B8 in which the butadiene and the solvent are separated and the residual butene is contained, Butene and the like to be mixed with the butene and then introduced into the oxidative dehydrogenation reaction part 410. This is preferable because the reaction can be continuously performed.

FIG. 5 is a view showing a state in which COx and O ₂ separated from the deasphalting part 560 are separated into the absorption and separation part 550 (FIG. 5) by replacing the discharge flow B11 generated after degassing with another discharge flow B11 ' The amount of the solvent required in the absorption separator 550 can be reduced by recondensing the hydrocarbons contained in the discharge stream B11 'after the degassing process by the condensation separator 530. [

The condensing system refers to a system that includes a compressor 531, a heat exchanger 532, and a condensation separator 530.

5, first, a reaction raw material containing butene, oxygen (O ₂ ), steam, and diluted gas (butane) is passed through an oxidative dehydrogenation reaction unit 510 to produce an oxidative dehydrogenation reaction including butadiene And flows into the cooling separator 520 along the flow B1 discharged in the reaction process. At this time, the starting material of the reaction joins with the discharge stream (B7) containing n-butane which is the diluent gas generated after the purification treatment in the purification process, flows into the oxidation dehydrogenation reaction unit (510) The reaction unit flows into the oxidative dehydrogenation reaction unit 510 by joining with the raw butene along the discharge flow B8.

The stream B 1 discharged from the reaction process may include butadiene, n-butane, butene, O ₂ , CO ₂ , H ₂ O and the like, and flows into the cooling separator 520 to separate water.

The exhaust stream B2 generated after the cooling and separation may include butadiene, n-butane, butene O ₂ , CO ₂ , and the like, and is introduced into the condensation separation unit 530.

The discharged stream B3 generated after the condensation separation includes the oxidation dehydrogenation reaction product containing condensed hydrocarbons after condensing the hydrocarbons by compression / cooling using cooling water or low temperature refrigerant in the condensation separation process And the effluent stream B4 'generated after the condensation separation may include hydrocarbons including condensed n-butane and butadiene.

COx and O ₂ can be further separated while passing through the deaeration section 560. A discharge flow (B11 ') occurs after the degassing can be re-condensed in the degassing (560) by adding In the COx and O ₂ separated by the condensing system separation section 530 condenses at, the after the degassing occurs another draw stream (B4 ") may be included in the crude hydrocarbon include n- butane, butene and butadiene, except for the COx and O ₂ separated by additional degassing at 560, fed to the purification unit 540 To purify the butadiene.

Generated in the absorption separation process draw stream (B5) is removed by selecting the hydrocarbons such as butadiene or part Tenryu included in the discharge flow (B3), including the separation in the condensate separation unit (530) O _2, COx and so on absorption and the remaining O _2, n- butane, butene, butadiene and the like may be included such as COx, another draw stream generated in the absorption separation process (B6 ') is separated from the absorbent unit 550, except for COx and O ₂ The contained crude hydrocarbons are absorbed by the solvent and are introduced into the deaeration section 560.

The discharged stream B7 generated after the butadiene separation and stagnation passing through the purifier 540 may be abundant in the remaining n-butane and forms a recycle flow to be fed into the oxidative dehydrogenation reactor 510 do. The solvent in the refining unit 540 can be separated and circulated to the absorption separator 550 (the discharge stream B9), and the discharge stream B8 in which the butadiene and the solvent are separated and the residual butane is contained, Butene and the like to be mixed with the butene and then introduced into the oxidative dehydrogenation reaction part 510, because the reaction can proceed continuously.

FIG. 6 is a view showing a state in which COx and O ₂ separated from the degassing part 660 are separated into the absorption and separation part 550 (FIG. 6) by replacing the discharge flow B11 generated after degassing with another discharge flow B11 ' It is possible to reduce the amount of solvent required in the absorption separator 650 by recondensing the hydrocarbons contained in the discharge stream B11 '

The condensing system refers to a system including a compressor 631, a heat exchanger 632, and a condensation separator 630.

6, first, a reaction raw material including butene, oxygen (O ₂ ), steam, and diluent gas (butane) is passed through an oxidative dehydrogenation reaction unit 610 to perform oxidation dehydrogenation reaction including butadiene And flows into the cooling separator 620 along the flow B1 discharged in the reaction process. At this time, a gas containing n-butane, which is a diluent gas generated after the purification treatment in the purification process, flows into the oxidative dehydrogenation reaction unit 610 along the discharge flow B7, The unreacted butenes join the raw butene along the discharge flow B8 and flow into the oxidative dehydrogenation reaction unit 610.

The stream B 1 discharged from the reaction step may include butadiene, n-butane, butene, O ₂ , CO ₂ , H ₂ O, etc., and flows into the cooling separator 620 to separate water.

The discharge flow B2 generated after the cooling and separation may include butadiene, n-butane, butene, O ₂ , CO ₂ , and the like, and is introduced into the condensation separation section.

The discharged stream B3 generated after the condensation separation includes the oxidation dehydrogenation reaction product containing condensed hydrocarbons after condensing the hydrocarbons by compression / cooling using cooling water or low temperature refrigerant in the condensation separation process And the exhaust stream B4 'generated after condensation separation may contain condensed n-butane, hydrocarbons including butene and butadiene, and is introduced into the deaeration section 660. [

Was passed through to the degassing (660) may be added to remove the COx and O ₂ the discharge flow (B11 ') it occurs after the degassing is added to the COx and O ₂ separated further from the degassing (660) to the condensate system and may be re-condensed in a separate condensation unit 630, the degassed and then generating another output flow (B4 "), the n- butane except for COx and O ₂ separated by additional degassing at 660, and butene Butadiene, and separates the high boiling point material from the crude hydrocarbons while passing through the high boiling point rejection 670, and the exhaust stream B4 "'generated in the high boiling point removal process contains crude hydrocarbons And the crude hydrocarbons may be passed through the purifier 640 to purify the butadiene.

As with Figure 4, the discharge flow (B5) include hydrocarbons such as butadiene or part Tenryu included in the discharge flow (B3), including the separation in the condensate separation unit (630) O _2, COx generated in the absorption separation process by the selective absorption is removed and can be included such as the remaining O _2, COx, occurs after the absorption separation another draw stream (B6 ') include n- butane, butene, except for COx and O ₂ on the absorption separation unit 650 And hydrocarbons including butadiene and the like are selectively absorbed in a solvent. The discharged stream B7 generated after the separation and purification of butadiene passing through the purification section 640 may be abundant in the residual n-butane to form a recycle stream to be fed into the oxidative dehydrogenation reaction section 610 .

The solvent can be separated from the refining section 640 and circulated to the absorption separating section 650 (the discharge flow B9), and the discharge stream B8 containing butadiene and the solvent separated and the residual butene, Butene and mixed with butene to the oxidative dehydrogenation reaction part 610. This is preferable because the reaction can be continuously performed.

Referring to FIG. 2, an oxidation dehydrogenation reaction unit 210 includes a reaction material containing butene, oxygen (O ₂ ), steam, and a diluent gas (butane) A cooling separation part 220 for separating water from the oxidative dehydrogenation reaction product containing butadiene obtained from the oxidative dehydrogenation reaction; A condensation separator 230 for condensing hydrocarbons from the oxidized dehydrogenation reaction product in which the water is separated; An absorption separator 250 for selectively absorbing and recovering hydrocarbons from the oxidative dehydrogenation reaction product containing hydrocarbons not condensed in the condensation separator 230; And a purifier 240 for separating butadiene from hydrocarbons containing n-butane, butene and butadiene condensed in the condensing separator 230. The purifier 240 separates butadiene from n The butane-containing gas is recycled to the oxidative dehydrogenation reaction unit 210, and the gas containing the butenes excluding the butadiene separated from the purification unit 240 is supplied to the oxidation dehydrogenation reaction unit 210 through the raw material Butene and a discharge stream B8 re-introduced into the oxidative dehydrogenation reaction unit 210 together with the butane.

A discharge flow (B6) is the condensate separation unit 230, which comprises in the absorption separation unit (250), n- butane, the hydrocarbon crude contains a butene and butadiene, etc., except for COx and O ₂ is absorbed in a solvent selected .

3, a reaction raw material containing butene, oxygen (O ₂ ), steam and diluent gas (butane) is passed through the oxidative dehydrogenation reactor 310 to oxidize A cooling separation section (320) for separating water from the oxidative dehydrogenation reaction product containing butadiene obtained from the dehydrogenation reaction; A condensation separator (330) for condensing hydrocarbons from the oxidized dehydrogenation reaction product in which the water is separated; An absorption separator 350 for selectively absorbing and recovering hydrocarbons from the oxidative dehydrogenation reaction product containing hydrocarbons not condensed in the condensation separator 330; And hydrocarbons and some COx, O in the discharge flow containing COx _2, O _2, including the n- butane, butene and butadiene condensed in the condensation separation unit (330), n- butane, butene and butadiene containing A deaerator 360 separating hydrocarbons; In the purification section 340, and includes a; and the degassing unit 360 of n- butane, purification unit 340 for separating butadiene from crude hydrocarbons including butene and butadiene, except for COx and O ₂ isolated from A discharge flow B9 in which the solvent is separated and circulated to the absorption separator 350 and a discharge flow B7 in which the gas containing n-butane except for butadiene and solvent is reintroduced into the oxidation dehydrogenation reactor 310 , And the gas including the butenes excluding the butadiene separated by the refining unit 340 is configured to have a discharge flow B8 that is reintroduced into the oxidative dehydrogenation reaction unit 310 together with the raw butene .

Containing the COx and O ₂ separated by the degassing unit 360 discharge flow (B11), n is other than the COx and O ₂ separated from the absorbing separating unit 350, circulated to the absorption separation unit 350, and (B6 ') comprising crude hydrocarbons including butane, butene and butadiene is configured to recycle to the deaeration section (360).

4, a reaction material containing butene, oxygen (O ₂ ), steam and diluent gas (butane) is passed through an oxidative dehydrogenation reaction unit 410 to oxidize A cooling separation section (420) for separating water from the oxidative dehydrogenation reaction product comprising butadiene obtained from the dehydrogenation reaction; A condensation separator (430) for condensing hydrocarbons from the oxidized dehydrogenation reaction product in which the water is separated; An absorption separation unit 450 for selectively absorbing and recovering hydrocarbons from the oxidative dehydrogenation reaction product containing hydrocarbons not condensed in the condensation separation unit 430; Including the n- butane, butene and butadiene and the hydrocarbon part contains the CO _2, in the discharge flow containing COx ₂ O, O ₂ and, n- butane, butene and butadiene condensed in the condensation separation unit 430 A deaeration section 460 for separating the hydrocarbons from the hydrocarbons; A high boiling point removing agent 470 for removing high boiling point materials from crude hydrocarbons including n-butane, butene and butadiene except COx and O ₂ separated from the deaeration section 460; And a purifier 440 for separating butadiene from crude hydrocarbons including n-butane, butene and butadiene from which a high boiling point material has been removed in the high boiling point remover 470. In the purifier 440, (B9) in which the solvent is separated and circulated to the absorption / separation unit 450, and a gas containing n-butane except for butadiene and a solvent in the purification unit 440 is supplied to the oxidation dehydrogenation reaction unit 410 The gas containing the butenes excluding the butadiene separated from the purifying section 440 is supplied to the oxidation dehydrogenation reaction section 410 together with the raw butene, (B8).

Containing the COx and O ₂ separated by the degassing (460) output flow (B11) n- butane, except for COx and O ₂ from the absorbing separating portion 450, and circulated to the absorption separation unit 450 (B6 ') containing crude hydrocarbons including butene, butadiene, and the like is selectively absorbed into the solvent is configured to be recycled to the deaeration section (460).

The discharge stream B4 "containing the crude hydrocarbons including n-butane, butene and butadiene separated from the deaeration section 460 is introduced into the high boiling point rejection 470, (B4 "') containing crude hydrocarbons from which point material has been separated is injected into the purifying section 440.

5, a reaction raw material containing butene, oxygen (O ₂ ), steam and diluent gas (butane) is passed through an oxidative dehydrogenation reaction unit 510 to oxidize A cooling separation section (520) for separating water from the oxidative dehydrogenation reaction product containing butadiene obtained from the dehydrogenation reaction; A condensation separator 530 for condensing hydrocarbons from the oxidized dehydrogenation reaction product in which the water is separated; An absorption separation unit 550 for selectively absorbing and recovering hydrocarbons from the oxidative dehydrogenation reaction product containing hydrocarbons not condensed in the condensation separation unit 530; A deaerator 560 for separating COx and hydrocarbons containing O ₂ and n-butane, butene and butadiene from the exhaust stream containing condensed hydrocarbons and some COx and O ₂ in the condensation separator 530; In the purification unit 540 comprises a, and; and the degassing 560. The COx and n- butane, butene and refining unit 540 to separate the butadiene from the crude butadiene hydrocarbon containing the excluding the O ₂ isolated from (B9) in which the solvent is separated and circulated to the absorption / separation unit 550, and the gas containing n-butane except for the butadiene and the solvent is discharged to the oxidation dehydrogenation reaction unit 510 , And the gas including the butenes excluding the butadiene separated from the purification unit 540 is configured to have a discharge flow B8 to be reintroduced into the oxidative dehydrogenation reaction unit 510 together with the raw butene .

Is introduced into the degassing 560, the discharge flow (B11 ') is condensed system include a a COx and O ₂ separated from the separately condensed material from the separation unit 530, condensed, separated from the absorption separation unit 550 a discharge flow (B6 ') for the crude hydrocarbons include n- butane, butene and butadiene, except for COx and O ₂ is included that the choice in the solvent absorption is configured to recycle to the degassing (560).

6, a reaction raw material containing butene, oxygen (O ₂ ), steam and diluent gas (butane) is passed through an oxidative dehydrogenation reaction unit 610 to oxidize A cooling separation section 620 for separating water from the oxidative dehydrogenation reaction product comprising butadiene obtained from the dehydrogenation reaction; A condensation separator (630) for condensing hydrocarbons from the oxidized dehydrogenation reaction product in which the water is separated; An absorption separator 650 for selectively absorbing and recovering hydrocarbons from the oxidative dehydrogenation reaction product containing hydrocarbons not condensed in the condensation separator 630; In the exhaust stream comprising a crude hydrocarbon and some CO _2, O _2, including the n- butane, butene and butadiene condensed in the condensation separation unit (630) COx and O _2, n- butane, butene and butadiene include A deaerator 660 for separating the crude hydrocarbons; And high boiling point remover 670 for removing high boiling substances from the crude hydrocarbon containing n- butane, butene and butadiene, except for the COx and O ₂ separated by the degassing (660); And a refining unit 640 for separating butadiene from crude hydrocarbons containing n-butane, butene and butadiene from which a high boiling point material is removed in the high boiling point refractory 670. In the refining unit 640, And the n-butane containing gas except for the butadiene and the solvent in the purifying section 640 is supplied to the oxidation dehydrogenation reaction section 610, The gas containing the butenes excluding the butadiene separated from the purifying section 640 is supplied to the oxidizing dehydrogenation reaction section 610 together with the raw butene, B8).

Of the discharge flow (B11 ') separated contain COx and O ₂ in the degassing (660) into the condensing system to condense re-separation unit (630) condensed, separated from the absorption separation unit (650) COx and n- butane, the hydrocarbon crude contains a butene and butadiene, except for O ₂ is discharged flow (B6 '), comprising a solvent selected in the absorbent is recycled to the de-configured to base 660.

The discharge stream B4 "containing the crude hydrocarbons containing n-butane, butene and butadiene separated from the deaerator 660 is introduced into the high boiling point rejection 670, The discharge stream B4 "'containing the crude hydrocarbons from which point components have been separated is configured to be introduced into the purifier 640.

The heat generated by incineration of the COx and O ₂ and the unabsorbed hydrocarbons separated from the absorption separating units 250, 350, 450, 550 and 650 causes the raw materials to heat up or the refining units 240 and 340 350, 450, 550, 650 and the oxidative dehydrogenation reaction units 210, 310, 410, 510, 610 so as to be recycled in the absorption separators 440, 540, (250, 350, 450, 550, 650) and the condensation separators (240, 340, 440, 540, 640) or the oxidative dehydrogenation Heat exchange means may be provided between the reactors 210, 310, 410, 510 and 610 and the condensation separators 240, 340, 440, 540 and 640.

By using the butadiene production method of the present invention and the production apparatus used therein, it is possible to complement the disadvantages of the production method using nitrogen as a diluting gas in a conventional butadiene production process and to increase the treatment effect, Thereby maximizing the energy efficiency. Also, since the butadiene production method of the present invention can be directly used for the purification / manufacture of various materials (ACN, NMP, DMF, etc.) described above, it can be applied to various processes.

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 spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

[ Example ]

Example  One

Oxygen was 1: 0.9, butene: water vapor = 1: 5, using raffinate-3 having the composition shown in Table 1 below as a raw material, using butane as a diluent gas, , Butene: butane = 1: 4 was obtained by oxidative dehydrogenation reaction. The water was removed from the cooling separator and the condensed water was discharged at a compression discharge temperature of 80 ° C , The pressure was 6.5KCG, the cooling temperature was 40 ° C, and the hydrocarbons were condensed by using a two-stage compressor and using cooling water.

Then, after absorption by using DMF as a solvent for recovering the butadiene contained in the uncondensed gas in the absorption separator, the butadiene loss to the discharge stream (B5) was reduced to about 0.5% A butadiene having a yield of 97.5% and a purity of 99.5% by weight was prepared.

At this time, the discharge flow of the oxidative dehydrogenation reaction part was measured by gas chromatography, and the composition in the discharge flows (B1 to B8) of the cooling separation part, the condensation separation part, the absorption separation part and the purification part was measured by a process simulator (AspenPlus) The results are shown in Table 2 below.

Example  2

The yield of final butadiene was 97.9% and the purity was 99.5% by weight from butene under the same conditions as in Example 1, except that the solvent was used so that the butadiene loss to the discharge stream (B5) in Example 1 was 0.1% Butadiene.

Comparative Example  One

Butadiene having a final butadiene yield of 89% and a purity of 99.5% by weight was prepared from butene under the same conditions as in Example 1, except for the step of absorption and separation in Example 1.

Comparative Example  2

The same procedure as in Example 1 was carried out except that the refrigerant was used in the step of absorption separation and separation in Example 1 and the condensation separation step to obtain a final butadiene yield of 96.5% and a purity of 99.5% by weight Butadiene.

[Test Example]

The amounts of energy consumption and butadiene loss in the condensation separation unit and the purification unit during the production of butadiene from butene in Examples 1 and 2 and Comparative Examples 1 and 2 were calculated by a process simulator (AspenPlus) and are shown in Table 4 below.

Furtherance mole% weight% 1-butene 0.00 0.00 Trans-2-butene 43.20 42.77 Cis-2-butene 28.80 28.51 n-butane 28.00 28.72

B1 B2 B3 B4 MW Kg / hr wt% Kg / hr wt% Kg / hr wt% Kg / hr wt% N2 28.0 0 0 0 0 1.6 0.2 0 0.0 CO2 44.0 145.5 2.2 145.5 3.0 196.6 25.2 0.3 0.0 CO 28.0 9.3 0.1 9.3 0.2 9.4 1.2 0.0 0.0 O2 32.0 73.8 1.1 73.8 1.5 74.6 9.6 0.0 0.0 butane 58.1 3740.0 57.1 3740.0 78.2 401.8 51.5 3548.8 81.5 1,3-butadiene 54.1 712.0 10.9 712.0 14.9 85.6 11.0 708.5 16.3 Butene 56.1 98.9 1.5 98.9 2.1 10.1 1.3 96.9 2.2 HB 72.1 11.3 0.2 0.0 0.0 0.0 0.0 0.0 0.0 water 18.0 1760.6 26.9 0.0 0.0 0.0 0.0 0.0 0.0 Sum 6551.6 100 4779.7 100 779.5 100 4354.6 100

B5 B6 B7 B8 1,3-butadiene Kg / hr wt% Kg / hr wt% Kg / hr wt% Kg / hr wt% Kg / hr wt% N2 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 CO2 145.2 34.2 56.8 15.7 0.0 0.0 0.0 0.0 0.0 0.0 CO 9.3 2.2 0.1 0.0 0.0 0.0 0.0 0.0 0.0 0.0 O2 73.8 17.4 1.2 0.3 0.0 0.0 0.0 0.0 0.0 0.0 butane 191.2 45.0 212.7 58.9 3548.8 99.5 0.0 0.0 0.0 0.0 1,3-butadiene 3.6 0.8 82.1 22.7 7.1 0.2 7.1 7.8 694.3 99.5 Butene 2.0 0.5 8.1 2.3 9.7 0.3 83.8 92.2 3.5 0.5 HB 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 water 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Sum 425.1 100 361.0 100 3565.6 100 90.8 100 697.8 100

As shown in Tables 2 and 3, in Example 1 of the present invention, the yield of butadiene was 99.5% by weight, which was much higher than that of Comparative Example 1, and 85.6 kg / hr of uncondensed butadiene in the condensation separation portion By recovering butadiene through absorption separation, the yield was improved by reducing the loss to 3.6 kg / hr, so that the economical efficiency was excellent.

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Condensation process and
Absorption process Condensation process and
Absorption process Condensation process Condensation process Condensation temperature
(° C) 40 40 40 0 butadiene
Loss (B5)
(Kg / hr) 3.6 0.7 62.7 10.9 condensation
Separating portion Refining part Condensation and
absorption
Separating portion Refining part condensation
Separating portion Refining part condensation
Separating portion Refining part vapor Gcal / hr 0.5 1.7 0.6 1.7 0.2 1.7 0.2 1.7 cooling water Gcal / hr 0.9 0.9 0.9 1.0 0.5 0.7 0.5 0.8 Refrigerant Gcal / hr 0.3 0.0 0.4 0.0 0.0 0.0 0.1 0.0 menstruum Ton / hr 2.2 12.2 3.3 12.2 0.0 14.5 0.0 14.5 Electricity kW 118.8 51.2 118.8 51.3 106.0 49.0 106.0 50.8

As shown in Table 4, in Examples 1 and 2 in which the absorption and separation were carried out after the condensation separation according to the present invention, the loss of butadiene in the flow B5 discharged from the absorption separation portion was remarkably reduced, thereby improving the economical efficiency. In Examples 1 and 2 in which the absorption and separation processes were performed, the butadiene loss was reduced and the butadiene recovery effect was more excellent than Comparative Example 2 in which the condensation temperature was lowered.

In Examples 1 and 2, although the butadiene loss in the discharge stream (B5) was much lower than that in Comparative Examples 1 and 2, the amount of solvent used in the condensation and absorption separation portion and the purification portion was similar to that of Comparative Examples 1 and 2 . This is because the exhaust stream containing the solvent that selectively absorbs butadiene in the absorption separator in Examples 1 and 2 flows into the purification unit through the condensation separation unit, and thus the amount of solvent required in the purification unit is reduced.

110, 210, 310, 410, 510, 610: oxidation dehydrogenation reaction unit
130, 250, 350, 450, 550, 650:
120, 320, 420, 520, 620:
230, 330, 430, 530, 630:
140, 240, 340, 440, 540, 640:
360, 460, 560, 660:
470, 670: high boiling point rejection
531, 631: Compressor
532, 632: heat exchanger

Claims (19)

Passing a reaction raw material including butene, oxygen (O ₂ ), steam and diluent gas through an oxidative dehydrogenation reaction unit to produce an oxidative dehydrogenation reaction product comprising butadiene,
Separating the water while passing the oxidative dehydrogenation reaction product containing the butadiene through the cooling separator,
Condensing the hydrocarbons while passing the oxidative dehydrogenation reaction product in which the water is separated to the condensation separation unit,
Separating COx and O ₂ while passing the oxidative dehydrogenation reaction product containing hydrocarbons not condensed in the condensation separator to the absorption separator,
The crude hydrocarbons containing n-butane, butene and butadiene condensed in the condensing and separating section are separated from the butadiene while being passed through the purification section, or passed through the deaeration section to further separate COx and O _2. Then, n-butane and butene And separating the butadiene while passing the crude hydrocarbon containing the butadiene through the purification section,
The n-butane-containing gas except the butadiene separated in the purifying section is re-introduced into the oxidative dehydrogenation reaction section,
Wherein the butadiene is separated from the refining part and the remaining butane-containing discharge stream is mixed with the raw butene and introduced into the oxidative dehydrogenation reaction part, wherein the diluent gas is butane. The method according to claim 1,
Wherein oxygen (O ₂ ) contained in the reaction raw material is introduced in a gas form having a purity of 90% or more. The method according to claim 1,
Wherein the reaction condition in the oxidative dehydrogenation reaction unit is a molar ratio of butene: oxygen: steam: diluent gas = 1: 0.5 to 3: 0.05 to 20: 0.05 to 20. The method according to claim 1,
Wherein said condensation separation is a one-stage compression structure, a one-stage to two-stage multi-stage compression structure, or a two-stage to ten-stage multi-stage compression structure, wherein the compression discharge temperature is 50 to 250 ° C. The method according to claim 1,
The refrigerant used in the condensation separation may be at least one selected from the group consisting of cooling water, ethylene glycol, an aqueous solution of ethylene glycol having a concentration of 20 to 100% by weight, propylene glycol, an aqueous propylene glycol solution having a concentration of 30 to 100% ≪ / RTI > The method according to claim 1,
Introducing COx and O ₂ further separated from the deaeration section into the absorption separation section,
The method of butadiene, characterized in that configured the crude hydrocarbon further comprises a n- butane and butadiene, except for COx and O ₂ separated in the degassing step to which the input part purified. The method according to claim 1,
Introducing COx and O ₂ further separated from the deaeration section into the absorption separation section,
Separating the crude hydrocarbons while passing the crude hydrocarbons including n-butane, butene and butadiene except for COx and O ₂ , which are further separated from the deaeration section, through high boiling point refuse,
And introducing the crude hydrocarbons separated from the high boiling point rejection into the refining section. The method according to claim 1,
Comprising the steps of: In the COx and O ₂ separated further from the degassing system into condensate,
Separating the crude hydrocarbons while feeding the crude hydrocarbons containing n-butane and butadiene except for COx and O ₂ , which are further separated from the deaeration section, into the purifier section or passing them through the high boiling point rejector, and then introducing the crude hydrocarbons into the purifier section; ≪ / RTI > The method according to claim 1,
Wherein the oxidative dehydrogenation reaction unit comprises butane, oxygen (O ₂ ), steam, and a gas containing n-butane recycled to the oxidative dehydrogenation reaction unit as a residue obtained by separating butadiene from the purification unit Characterized in that it is driven under a isothermal or adiabatic condition at a reaction temperature of 150 to 650 占 폚 using a ferrite catalyst or an iron catalyst as a reaction raw material. The method according to claim 1,
Wherein the cooling separator is driven by a quencher or an indirect cooling method of quenching. The method according to claim 1,
The absorption separation method of the butadiene portion, characterized in that driven by absorption method using a solvent capable of selectively absorbing for separating COx and O _2. The method according to claim 1,
Wherein the deaeration section is driven by stripping or degassing using a general column. The method according to claim 1,
Wherein the absorption separator comprises: a discharge flow in which crude hydrocarbons including n-butane and butadiene except for COx and O ₂ are re-introduced into a condenser separation unit or a deaeration unit; Wherein the butadiene is formed to have the same structure as the butadiene. An oxidative dehydrogenation reaction unit for obtaining an oxidative dehydrogenation reaction product containing butadiene by oxidative dehydrogenation of a reaction raw material including butene, oxygen (O ₂ ), steam and diluent gas;
A cooling separator for separating water from the oxidative dehydrogenation reaction product comprising butadiene obtained from the oxidative dehydrogenation reaction;
A condensation separator for condensing hydrocarbons from the oxidized dehydrogenation reaction product in which the water is separated;
An absorption separator for separating COx and O ₂ from the oxidative dehydrogenation reaction product containing hydrocarbons not condensed in the condensation separation unit; And
And a purifier for separating butadiene from the crude hydrocarbons containing n-butane, butene and butadiene condensed in the condensation separator,
The n-butane-containing gas except the butadiene separated in the purifying section is re-introduced into the oxidative dehydrogenation reaction section,
Wherein the butadiene is separated from the refining part and the remaining butene is mixed with the raw butene, and is introduced into the oxidative dehydrogenation reaction part, wherein the diluent gas is butane. 15. The method of claim 14,
And an exhaust stream to which n-butane and butadiene-containing hydrocarbons except for COx and O ₂ separated from the absorption separation section are supplied to the deaeration section. 15. The method of claim 14,
Degassing to remove the n- butane, butene and butadiene and COx and O ₂ in the crude hydrocarbon include, n- butane, the hydrocarbon crude contains a butene and butadiene, except for COx and O ₂ separated from the absorbing separating section; And an exhaust stream for re-introducing COx and O ₂ separated from the deaeration section to the absorption separation section. 15. The method of claim 14,
Degassing to remove the n- butane, butene and butadiene and COx and O ₂ in the crude hydrocarbon include, n- butane, the hydrocarbon crude contains a butene and butadiene, except for COx and O ₂ separated from the absorbing separating section; And a discharge flow for introducing COx and O ₂ separated from the deaeration section into a condensing system. 18. The method according to claim 16 or 17,
A high boiling point rejection for separating high boiling point components from the crude hydrocarbons containing n-butane, butene and butadiene separated from the deaeration section; And
And an exhaust stream to which crude hydrocarbons separated from the high boiling point rejection are introduced into the purification section. 15. The method of claim 14,
An exhaust stream in which the solvent separated from the purification section is circulated to the absorption and desorption section, and a discharge stream in which n-butane-containing gas excluding butadiene and solvent is reintroduced into the oxidative dehydrogenation reaction section. Manufacturing apparatus.

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