KR102246175B1 - Method for producing conjugated diene - Google Patents

Abstract

The present invention relates to a method and apparatus for producing butadiene.According to the present invention, in the production of butadiene through oxidative dehydrogenation of butene, butane is used instead of nitrogen as a dilution gas, hydrocarbons and gases including C4 mixtures, etc. Since butadiene can be easily separated from the reaction product composed of, there is an effect of providing a method for producing butadiene and an apparatus for safely securing high-purity butadiene and economical efficiency of the process, such as energy and raw material cost reduction and productivity improvement.

Description

Butadiene manufacturing method {METHOD FOR PRODUCING CONJUGATED DIENE}

The present invention relates to a method for producing butadiene, and more particularly, to a method for producing butadiene capable of securing a high purity butadiene and economical efficiency of a process such as energy and raw material cost reduction and productivity improvement.

Butadiene is used as an intermediate of many petrochemical products in the petrochemical market, and its demand and value are gradually increasing as one of the most important basic oils in the petrochemical market.

Methods of preparing butadiene include extraction from C4 fraction through naphtha cracking, direct dehydrogenation of butene, and oxidative dehydrogenation of butene.

Among them, the method of producing butadiene through oxidative dehydrogenation of butene uses oxygen as a reactant to remove two hydrogens from butene to produce butadiene.Since stable water is produced as a product, it is very thermodynamically It is advantageous, and since it is an exothermic reaction unlike the direct dehydrogenation reaction, a high yield of butadiene can be obtained even at a lower reaction temperature compared to the direct dehydrogenation reaction. A method of producing butadiene through oxidative dehydrogenation of butene may be an effective method capable of meeting the increasing demand for butadiene.

On the other hand, in the oxidative dehydrogenation method of butene as described above, in addition to raw materials for the purpose of reducing the risk of explosion due to oxygen and removing reaction heat, nitrogen, steam, etc. are mainly used as a dilution gas. And a method of absorbing hydrocarbons in the reaction product using a solvent when separating hydrocarbons from reaction products containing light gases (COx, O _{2, etc.) and hydrocarbons, and liquefying hydrocarbons by cooling the reaction product.} Among the methods, the absorption method is mainly used. This is because the method of liquefying and separating the reaction product requires a cryogenic refrigerant during liquefaction due to the dilution gas and light gas flows present in the reaction product, which increases the equipment cost and operation cost, making it difficult to secure the economics of the process. This is because.

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

Referring to FIG. 1, an oxidation dehydrogenation reaction unit 110 for generating an oxidative dehydrogenation reaction product including butadiene from a reaction raw material including _{butene, oxygen (O 2 ), steam, and nitrogen as a diluted gas;} A cooling separation unit 120 for separating water from the reaction product obtained from the oxidative dehydrogenation reaction; An absorption separation unit 130 for separating butadiene or a C4 mixture including butadiene and hydrocarbons from the oxidation dehydrogenation product from which water is separated; And a purification unit 140 for separating butadiene from a stream containing butadiene separated by the absorption and separation unit 130.

The oxidative dehydrogenation reaction unit 110 ferrites a reaction raw material containing _{butene, oxygen (O 2} ), steam, dilute gas (N _{2 ), and unreacted butenes recovered from the purification unit.} It may be driven under isothermal or adiabatic conditions using a catalyst based on or bismuth molybdate.

The cooling separation unit 120 may be driven by a direct cooling method (quencher) of rapid cooling or an indirect cooling method.

1 is an example in which only butadiene is selectively absorbed and separated by the absorption and separation unit 130, but the absorption and separation unit 130 selectively absorbs only butadiene from the oxidation dehydrogenation reaction product from which water is removed, or hydrocarbons including a C4 mixture. It may be driven in an absorption method using a solvent capable of absorbing the whole. Examples of the selective absorption solvent include ACN (Acetonitrile), NMP (N-methylpyrrolidone), DMF (Dimethyl formamide), and the like, and the total absorption solvent may include toluene and xylene. _{The COx and O 2} separated by the absorption and separation unit 130, and _{N 2} used as a dilution gas are completely incinerated, or in some cases, some are recovered and reused in the reaction unit, and some are incinerated.

The purification unit 140 is, for example, an Acetonitrile process, an N-methylpyrrolidone (NMP) process, or a dimethyl formamide (DMF) process as a conventional butadiene purification apparatus, and is driven in a partially modified form of the process as needed. Butadiene can be purified.

However, the absorption separation process 130 mostly uses an excess of solvent, and a large amount of energy is used in the process of recovering the absorption solvent and in the process of recovering and purifying butadiene in the purification unit 140. In addition, even if the absorption separation process is replaced with a condensation separation process, a cryogenic refrigerant is required, and the economic feasibility of the process, such as energy, raw material cost, and production cost, cannot be secured. Therefore, the development of related technologies that can improve this is urgently needed.

Korean Patent Application Publication No. 2012-0103759

In order to solve the problems of the prior art as described above, the present invention uses butane instead of nitrogen as a diluent gas when preparing butadiene through oxidative dehydrogenation of butene, and is used to separate butadiene from oxidative dehydrogenation reaction products when conventional nitrogen is used. A condensation separation method is provided in which butadiene is liquefied and separated using a low-temperature refrigerant or cooling water instead of the conventional absorption separation method. In particular, in order to minimize the loss of active ingredients (referring to all hydrocarbons including butadiene) discharged along with the flow containing _{COx, O 2} , and n-butane separated in the condensation separation process, active ingredients from the upper stream of the condensation process An object of the present invention is to provide a method for producing butadiene to which a method of recovering the whole is applied.

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

In order to achieve the above object, the present invention

Obtaining an oxidative dehydrogenation reaction product containing butadiene obtained by passing a reaction raw material containing butene, oxygen (O _{2 ), steam, and a diluted gas through an oxidation dehydrogenation reaction unit, and}

Separating water while passing the oxidative dehydrogenation reaction product including the butadiene through a cooling separation unit,

Condensing hydrocarbons while passing the oxidative dehydrogenation reaction product from which the water is separated through a condensation separator,

Recovering the entire hydrocarbons that have not been condensed in the condensation separation unit in the presence of a non-combustible diluent gas while passing an oxidation dehydrogenation reaction product including hydrocarbons that have not been condensed in the condensation separation unit through the absorption separation unit,

And separating butadiene while passing hydrocarbons containing n-butane, butene and butadiene condensed in the condensation separation unit through a purification unit,

Gas containing n-butane excluding butadiene separated by the refining unit by introducing a non-flammable dilution gas into the flow of transferring the oxidative dehydrogenation reaction product including hydrocarbons not condensed in the condensation separation unit to the absorption separation unit Is reintroduced into the oxidation dehydrogenation reaction unit, butadiene is separated from the purification unit, and the remaining butene is mixed with raw material butene and introduced into the oxidation dehydrogenation reaction unit, wherein the dilution gas is butane. It provides a method for producing butadiene.

In addition, the present invention is an oxidative dehydrogenation reaction unit for oxidative dehydrogenation of a reaction raw material including _{butene, oxygen (O 2 ), steam and dilute gas;} A cooling separation unit for separating water from an oxidative dehydrogenation reaction product containing butadiene obtained from the oxidative dehydrogenation reaction;

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

An absorption separation unit for separating _{COx and O 2} and non-combustible diluting gas in the presence of a non-combustible diluent gas from an oxidation dehydrogenation reaction product including hydrocarbons that are not condensed in the condensation separation unit; And

A purification unit for separating butadiene from crude hydrocarbons including n-butane, butene and butadiene condensed in the condensation and separation unit and n-butane, butadiene and butadiene recovered from the absorption and separation unit; Including,

Gas containing n-butane excluding butadiene separated from the purification unit is re-introduced to the oxidation dehydrogenation reaction unit, and butadiene is separated from the purification unit and the remaining butene is mixed with raw material butene to undergo the oxidative dehydrogenation reaction. It provides an apparatus for producing butadiene, characterized in that it is introduced as a part.

According to the present invention, butane is used instead of nitrogen as a diluting gas in the production of butadiene through oxidative dehydrogenation of butene. Through the condensation separation method that liquefies and separates the hydrocarbons and the absorption separation method that recovers the entire hydrocarbons flowing to the upper stream after condensation, the loss of hydrocarbons is minimized to reduce energy and raw material costs and improve productivity, thereby ensuring the economical efficiency of the process and high-purity butadiene. It is an object of the present invention to provide a method for producing butadiene that can be secured.

1 is a view for explaining a conventional butadiene manufacturing apparatus and method.
2 to 6 are views for explaining the butadiene manufacturing apparatus and manufacturing method according to the present invention.
7 is a view showing the oxygen concentration in the main flow and the explosion region in the absorption and separation unit of Example 1 and Comparative Examples 1 and 2 according to the present invention.

Hereinafter, the method and apparatus for producing butadiene of the present invention will be described in detail. The method and apparatus for manufacturing butadiene of the present invention are characterized in that an absorption separation process is applied to recover the entire active ingredient in the flow that flows out through the upper part of the condensation separation process and the condensation separation process by using butane as a diluting gas. In this way, if butane is used as a dilution gas, the condensation separation unit can separate hydrocarbons from the oxidation dehydrogenation reaction product even with a low-temperature refrigerant or cooling water, and the absorption separation unit recovers all hydrocarbons flowing out to the outside of the system. It is possible to economically manufacture butadiene by minimizing the active ingredients that are spilled into the furnace.

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

Referring to FIG. 2, first, _{an oxidative dehydrogenation reaction product including butadiene by passing a reaction raw material including butene, oxygen (O 2} ), steam, and a diluted gas (butane) through an oxidation dehydrogenation reaction unit 210 Get At this time, the reaction raw material may be introduced into the oxidative dehydrogenation reaction unit 210 by merging with the discharge streams (B7, B8) generated after being purified in the purification process, and the flow (B1) discharged from the process includes butadiene. , n-butane, butene, O ₂ , COx, H ₂ O, etc. may be included.

The flow B1 discharged from the oxidative dehydrogenation reaction flows into the cooling separation unit 220 to separate water.

The discharge flow B2 generated after the cooling separation may contain butadiene, n-butane, butene, O ₂ , COx, etc., and flow into the condensation separation unit 230.

The discharge stream (B3) generated after the condensation separation may include an oxidative dehydrogenation reaction product including uncondensed hydrocarbons after condensing hydrocarbons through compression/cooling using cooling water or the like in the condensation separation process, It flows into the absorption and separation unit 250 to recover hydrocarbons. Another discharge stream (B4) generated after the condensation separation may include n-butane condensed in the condensation separation unit 230, and crude hydrocarbons including butene and butadiene, and the butadiene is purified in the purification unit 240 can do.

In the flow of the oxidation dehydrogenation reaction product including hydrocarbons that are not condensed in the condensation separation unit 230 to be transferred to the absorption separation unit 250, a non-flammable dilution gas may be introduced. In this case, in the absorption separation process Stability can be ensured by preventing the composition of the gaseous phase generated from entering the explosive area.

The discharge stream (B5) generated in the absorption separation process _{may contain non-flammable diluent gases such as O 2} and COx separated in the previous condensation separation process, and another discharge flow (B6) generated after absorption separation includes an absorption separation unit ( 250), except for COx and O ₂ , may contain crude hydrocarbons including n-butane, butene and butadiene, and pass through the purification unit 240 to separate butadiene.

The discharge stream (B7) generated after the purification may contain an abundant amount of remaining n-butane, and a recycle stream that is introduced into the oxidative dehydrogenation reaction unit 210 is formed.

The butadiene is separated from the purification unit 240 and the discharge flow (B8) including the remaining butene may be mixed with the raw material butene to form a recycle flow introduced into the oxidative dehydrogenation reaction unit 210, and this In this case, since the reaction can proceed continuously, there is an effect of excellent productivity.

The “crude hydrocarbon” refers to a crude hydrocarbon commonly used in this technical field, and unless otherwise specified, a hydrocarbon containing butadiene obtained from an oxidative dehydrogenation reaction product as a raw material for the refining unit Refers to.

The term “COx” refers to _{CO, CO 2 unless otherwise specified.}

The butene may be 1-butene, 2-butene, or a mixture thereof. The raw material containing butene is not particularly limited if it is a raw material containing butene that can be used in the production of butadiene in general.

For example, the butene may be obtained from a hydrocarbon mixture containing butenes such as raffinate-2 and raffinate-3 among high-purity butenes and C4 fractions produced by naphtha decomposition.

The steam is a gas that is introduced for the purpose of reducing the risk of explosion of reactants in the oxidative dehydrogenation reaction, preventing coking of the catalyst and removing reaction heat.

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

The catalyst filled in the reactor is not particularly limited as long as it is capable of producing butadiene by oxidative dehydrogenation of butene, and may be, for example, a ferrite catalyst or a bismuth molybdate catalyst.

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

The dilution gas may be butane.

The non-flammable dilution gas may be, for example, nitrogen gas (N ₂ ), argon, helium or carbon dioxide (CO ₂ ), preferably nitrogen gas, in this case oxygen (O ₂ ) and hydrocarbons such as n-butane The explosive range can be avoided by lowering the mole fraction of.

The oxidative dehydrogenation reaction unit 210 is, for example, _{a residue from which butene, oxygen (O 2} ), steam, and butadiene are separated from the purification unit 240 and is used as the oxidative dehydrogenation reaction unit. It may be driven under isothermal or adiabatic conditions using a ferritic catalyst using n-butane and butene as reaction raw materials.

As an example, oxygen (O ₂ ) contained in the reaction raw material may be introduced in the form of 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, through which the amount of active ingredients is measured in real time and the reaction is introduced into the reactor. The amount of ingredients contained in the raw material can be individually adjusted.

For example, the reaction conditions in the oxidative dehydrogenation reaction unit 210 may be a molar ratio of butene: oxygen: water vapor: diluted gas (n-butane) = 1: 0.5 to 3: 0.1 to 20: 0.1 to 20, and this range It can achieve excellent economics of the process, such as energy and raw material cost reduction and productivity improvement.

As a specific example, the oxidative dehydrogenation reaction unit 210 includes a molar ratio of oxygen:butene of 0.5-3:1, a molar ratio of water vapor:butene of 1-20:1, a molar ratio of n-butane:butene of 0.1-20:1, and a reaction pressure of normal pressure. It is preferable to be driven under isothermal or adiabatic conditions of ~10atm, reaction temperature of 150~650℃, and within this range, it is possible to achieve excellent economics of the process, such as energy and raw material cost reduction and productivity improvement.

The cooling separation unit 220 may be driven by a direct cooling method of rapid cooling or an indirect cooling method, for example, and the rapid cooling temperature may be 0 to 100°C.

The condensation separation unit 230 may have a single compression structure of 1 stage, a multistage compression structure of 2 to 10 stages, or a multistage compression structure of 1 stage to 2 stages, for example. The reason for the multi-stage compression is that when compressing from the initial pressure to the target pressure at one time, not only a lot of power is required, but also heat is generated by gas compression, which causes the gas to expand and the compression efficiency decreases. In order to prevent this, multi-stage compression is performed, and the heat generated in the compression process can be cooled using a cooler.

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

In one embodiment of the present invention, the refrigerant used in the condensation separation unit 230 is cooling water, ethylene glycol, an aqueous solution of ethylene glycol having a concentration of 20 to 100% by weight, propylene glycol, an aqueous solution of propylene glycol having a concentration of 30 to 100% by weight, and It may be one or more selected from the group consisting of propylene-based solvents.

The propylene-based solvent is, for example, propylene or a compound containing propylene, and may be a material having a boiling point of -10°C or less, or -10 to -50°C.

The refrigerant may be preferably cooling water, 0 to 40°C cooling water, or 5 to 30°C, and in this case, the extrusion discharge temperature may be 250°C or less, or 50 to 200°C, and the compressed discharge flow The cooling temperature may be 120°C or less, or 20 to 80°C.

Conventionally, nitrogen is used as the dilution gas, and a cryogenic refrigerant is required when separating the dilution gas and the light gas stream by the condensation method, but in the present invention, a lower grade refrigerant is also possible by introducing butane as the dilution gas. It is done.

The purification unit 240 may be applied to a conventional apparatus for purifying butadiene, for example, ACN (Acetonitrile) process, NMP (N-methylpyrrolidone) process, or DMF (Dimethyl formamide) process.

The absorption separation unit 250 may be driven by an absorption method using, for example, toluene, xylene, or the like as a solvent for absorbing the entire hydrocarbons.

A non-flammable dilution gas may be introduced into the discharge flow through which the oxidation dehydrogenation reaction product including hydrocarbons not condensed in the condensation separation unit 230 is transferred to the absorption separation unit 250.

The presence of non-flammable diluent gas in the absorption and separation unit 250 ensures that the concentration of hydrocarbons is greater than or equal to the lower explosion limit, or the oxygen concentration is less than or equal to the limit oxygen concentration, thereby eliminating the possibility of explosion in the absorption and separation unit to secure stability. It is characterized in that to be able to.

The butadiene obtained through the separation step may be recovered as high purity butadiene by removing the solvent, the high boiling point and the low boiling point components through the purification step.

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

3 to 9 show that the oxidative dehydrogenation reaction product from which water is separated by passing through the cooling separation unit 220 in FIG. 2 is introduced into the purification unit 240 through the coagulation separation unit 230 and the absorption separation unit 250 It is a subdivided process (emission flows B4, B6) including a degassing unit and a solvent recovery unit.

The degassing unit and the solvent recovery unit may be driven, for example, by stripping or degassing using a conventional column.

Referring to FIG. 3, first, _{a reaction raw material containing butene, oxygen (O 2} ), steam, and a dilute gas (butane) is passed through an oxidation dehydrogenation reaction unit 310, and an oxidative dehydrogenation reaction containing butadiene. The product is obtained. In this case, the oxidative dehydrogenation reaction product may be introduced into the oxidative dehydrogenation reaction unit 310 by joining with the discharge streams B7 and B8 generated after being purified in the purification process. The flow B1 discharged from the process may contain butadiene, n-butane, butene, O ₂ , COx, H ₂ O, etc., and water is separated by flowing into the cooling separation unit 320.

The discharge flow B2 generated after the cooling separation may contain butadiene, n-butane, butene, O ₂ , COx, etc., and flow into the condensation separation unit 330.

The discharge stream (B3) generated after the condensation separation may include an oxidative dehydrogenation reaction product including uncondensed hydrocarbons after condensing hydrocarbons through compression/cooling using cooling water or the like in the condensation separation process, It flows into the absorption separation unit 350.

Another discharge stream (B4') generated after the condensation separation may include an oxidative dehydrogenation reaction product including hydrocarbons containing n-butane, butene and butadiene condensed in the condensation separation unit, and a degassing unit ( 360) and COx and O ₂ are separated.

The discharge stream (B5) generated in the absorption separation process _{may contain a non-flammable diluent gas such as O 2} and COx separated in the previous condensation separation process, and the discharge flow (B6') generated after the absorption separation includes an absorption separation unit ( In 350), _{hydrocarbons including n-butane, butene and butadiene excluding COx and O 2} may be entirely absorbed and included in the solvent, and the solvent is recovered by passing through the solvent recovery unit 370, and the recovered solvent is It can be re-introduced into the absorption and separation unit 350 through the discharge flow B9.

Another discharge stream (B10) generated in the solvent recovery process may include hydrocarbons including n-butane, butene and butadiene from which the solvent has been removed, and COx and O ₂ are passed through the degassing unit 360. Can be further separated.

The discharge stream (B4") generated after the degassing may contain crude hydrocarbons including n-butane, butene and butadiene, excluding _{COx and O 2 further separated in the degassing unit 360, and the purification unit 340} ) To separate butadiene.

The discharge stream (B7) generated after the purification may contain an abundant amount of remaining n-butane, and a recycle stream introduced into the oxidative dehydrogenation reaction unit 310 is formed.

The butadiene is separated from the purification unit 340 and the discharge stream (B8) containing the remaining butene is combined with the raw material butene to form a recycle stream that is introduced into the oxidation dehydrogenation reaction unit 210.

The non-flammable dilution gas may be, for example, nitrogen gas (N ₂ ), argon, helium or carbon dioxide (CO ₂ ), preferably nitrogen gas, in this case oxygen (O ₂ ) and hydrocarbons such as n-butane The explosive range can be avoided by lowering the mole fraction of.

4 is an additional discharge flow (B4"') to the discharge flow (B4") generated after degassing in FIG. 3, and the discharge flow (B4") is further separated from the degassing unit 460. Hydrocarbons containing n-butane, butene butadiene, and high boiling point substances excluding COx and O ₂ may be included, and high boiling point substances are separated from the high boiling point removal unit 480, and discharge generated after the high boiling point removal process The stream (B4"') may contain crude hydrocarbons including n-butane, butene and butadiene from which the high boiling point material has been removed, and is introduced into the purification unit 440 to be purified.

The high boiling point removal unit may be driven by a distillation method, for example.

The high boiling point substance may be, for example, an aromatic hydrocarbon such as furan, aldehyde, acetic acid, benzene, or phenol, or styrene.

Referring to FIG. 4, first, _{a reaction raw material including butene, oxygen (O 2} ), steam, and a dilute gas (butane) is passed through an oxidation dehydrogenation reaction unit 410, and an oxidative dehydrogenation reaction including butadiene. The product is obtained. At this time, the reaction raw material may be introduced into the oxidative dehydrogenation reaction unit 410 by joining with the discharge streams B7 and B8 generated after being purified in the purification process. The flow B1 discharged from the process may contain butadiene, n-butane, butene, O ₂ , COx, H ₂ O, etc., and water is separated by flowing into the cooling separation unit 420.

As in FIG. 3, the discharge flow B2 generated after the cooling separation may contain butadiene, n-butane, butene, O ₂ , COx, etc., and flow into the condensation separator 430.

The discharge stream (B3) generated after the condensation separation process may contain an oxidative dehydrogenation reaction product including uncondensed hydrocarbons after condensing hydrocarbons through compression/cooling using cooling water or the like in the condensation separation process. It flows into the separating part 450.

The discharge stream (B3) generated after the condensation separation is transferred to the absorption and separation unit 450, while a non-flammable dilution gas is introduced.

The non-flammable dilution gas may be, for example, nitrogen gas (N ₂ ), argon, helium or carbon dioxide (CO ₂ ), preferably nitrogen gas, in this case oxygen (O ₂ ) and hydrocarbons such as n-butane The explosive range can be avoided by lowering the mole fraction of.

The discharge flow (B5) generated in the absorption separation process _{may contain a non-flammable dilution gas such as COx and O 2} separated in the previous condensation separation process, and the discharge flow (B6') generated in the absorption separation process includes an absorption and separation unit. Hydrocarbons including n-butane, butene and butadiene excluding COx and O ₂ in may be completely absorbed into the solvent, and the solvent is recovered by passing through the solvent recovery unit 470, and the recovered solvent May be re-transmitted to the absorption and separation unit 450 through the discharge flow B9.

The discharge stream (B10) generated after the solvent recovery and the discharge stream (B4') including the hydrocarbons condensed in the condensation separation unit are passed through the degassing unit 460 to further separate _{COx and O 2.} I can. The discharge stream (B11) generated in the degassing process may contain COx and O ₂ additionally separated from the degassing unit 460, and may be absorbed and separated by being introduced into the absorption and separating unit 460, which is generated after the degassing. Another discharge stream (B4") that has been further separated from the degassing unit 460 may include n-butane, butene and butadiene, and crude hydrocarbons containing high-boiling substances, excluding _{COx and O 2 further separated from the degassing unit 460, and high boiling point agents} It is introduced into the rejection 480 to separate the high boiling point material.

In the discharge stream (B4"') generated after the high boiling point removal process, a crude hydrocarbon containing n-butane, butene and butadiene from which the high boiling point material has been removed may be introduced into the refining unit 440.

The high boiling point substance may be, for example, aromatic hydrocarbons such as benzene, styrene, and phenol, butadiene dimer, acetopinone, benzopinone, or anthrequinone.

The butadiene may be separated by passing through the purification unit 440, and the remaining n-butane may be abundantly included in the discharge stream B7 generated after the purification, and introduced into the oxidative dehydrogenation reaction unit 410 Can form a recirculating flow.

The butadiene is separated from the purification unit 340 and the discharge flow B8 including the remaining butene may form a recycle flow introduced into the oxidative dehydrogenation reaction unit 410.

5 is a replacement of the discharge flow (B11) generated after degassing of FIG. 3 with another discharge flow (B11'), and _{gas separation by introducing COx and O 2} separated from the degassing unit 560 into the condensation system. Efficiency can be improved.

Unless otherwise specified, the condensation system refers to a system including a compressor 531, a heat exchanger 532 and a condensation separator 530.

Referring to FIG. 5, first _{, oxidative dehydrogenation containing butadiene obtained by passing a reaction raw material containing butene, oxygen (O 2} ), steam, and dilute gas (butane) through an oxidation dehydrogenation reaction unit 510 A reaction product is obtained. At this time, the reaction raw material may be introduced into the oxidative dehydrogenation reaction unit 510 by joining with the discharge streams (B7, B8) generated after being purified in the purification process, and the flow (B1) discharged from the reaction process Butadiene, n-butane, butene, O ₂ , COx, H ₂ O, etc. may be included, and the water is separated by flowing into the cooling separation unit 520.

The discharge flow B2 generated after the cooling separation may contain butadiene, n-butane, butene, O ₂ , COx, etc., and flow into the condensation separation unit 530.

The discharge stream (B3) generated after the condensation separation may contain an oxidative dehydrogenation reaction product including hydrocarbons that are not condensed after condensing through compression/cooling of hydrocarbons using cooling water in the condensation separation process, and the discharge The flow B3 flows into the absorption and separation unit 550.

In the discharge stream (B3) containing the oxidative dehydrogenation reaction product including hydrocarbons that are not condensed in the condensation separation unit 530, a non-flammable dilution gas is introduced while flowing into the absorption separation unit 550.

Another discharge stream (B4') generated after the condensation separation may contain an oxidative dehydrogenation reaction product including condensed n-butane, hydrocarbons including butene and butadiene, and to the degassing unit 560 It flows in and separates _{COx and O 2.}

The discharge flow (B5) generated in the absorption separation process _{may contain a non-flammable diluent gas such as COx and O 2} separated in the previous condensation separation process, and another discharge flow (B6') generated in the absorption separation process is absorbed. In the separation unit 550, _{hydrocarbons including n-butane, butene and butadiene, excluding COx and O 2} are completely absorbed in the solvent, and pass through the solvent recovery unit 570 to recover the solvent, and the recovery The resulting solvent may be re-introduced into the absorption and separation unit 550 through the discharge flow B9.

_{COx and O 2} are added while passing another discharge stream (B10) generated in the solvent recovery process and a discharge stream (B4') containing hydrocarbons condensed in the condensation separation unit through the degassing unit 560 Can be separated by

The discharge flow (B11') generated after the degassing _{contains COx and O 2} additionally separated from the degassing unit 560, and is introduced into the condensation system and recondensed at the condensation separation unit 530 in the condensation system. It can be separated, and another discharge stream (B4") generated after the degassing includes crude hydrocarbons including n-butane, butene and butadiene excluding _{COx and O 2 further separated in the degassing unit 560} May be passed through the purification unit 540 to separate butadiene.

Unless otherwise specified, the condensation system refers to a system including a compressor 531, a heat exchanger 532, and a condensation separator 530.

The discharge stream B7 generated after the purification may contain an abundant amount of remaining n-butane, and a recycle stream introduced into the oxidation dehydrogenation reaction unit 510 is formed. In another discharge stream (B8) generated after the purification, butadiene is separated from the purification unit 540 and the remaining butene may be included, and recycle that is mixed with raw material butene and injected into the oxidative dehydrogenation reaction unit 510 Flow can be formed.

6 is a replacement of the discharge flow (B11) generated after degassing of FIG. 4 with another discharge flow (B11'), and the COx and O ₂ separated from the degassing unit 660 are introduced into the condensing system to separate the condensation separator. As it is circulated to 630, the gas separation efficiency can be improved.

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

Referring to FIG. 6, first, _{a reaction raw material including butene, oxygen (O 2} ), steam, and a dilute gas (butane) is passed through an oxidation dehydrogenation reaction unit 610, and an oxidative dehydrogenation reaction including butadiene. The product is obtained.

At this time, the reaction raw material may be introduced into the oxidative dehydrogenation reaction unit 610 by joining with the discharge streams B7 and B8 generated after being purified in the purification process. The flow (B1) discharged from the reaction process may include butadiene, n-butane, butene, O ₂ , COx, H ₂ O, and the like, and the discharge flow (B1) is introduced into the cooling separation unit 620 and water Is separated.

As in FIG. 5, the discharge flow B2 generated after the cooling separation may contain butadiene, n-butane, butene, O ₂ , COx, etc., and water is separated by flowing into the condensation separator 630.

The discharge stream (B3) generated after the condensation separation may include an oxidative dehydrogenation reaction product including uncondensed hydrocarbons after condensing hydrocarbons through compression/cooling using cooling water or the like in the condensation separation process. The discharge flow (B3) is introduced into the absorption and separation unit 650, while flowing into the absorption and separation unit 650, a non-flammable dilution gas may be introduced.

The non-flammable dilution gas may be, for example, nitrogen gas (N ₂ ), argon, helium or carbon dioxide (CO ₂ ), preferably nitrogen gas, in this case oxygen (O ₂ ) and hydrocarbons such as n-butane The explosive range can be avoided by lowering the mole fraction of.

The discharge flow (B5) generated in the absorption separation process may include COx and O ₂ separated from the previous condensation separation process, and a non-flammable diluent gas, and another discharge flow (B6') generated in the absorption separation process is absorbed. In the separation unit 650, _{hydrocarbons including n-butane, butene and butadiene excluding COx and O 2} may be completely absorbed into the solvent, and the solvent is recovered by passing through the solvent recovery unit 670. , The recovered solvent may be re-permeable to the absorption and separation unit 650 through the discharge flow B9.

Another discharge flow (B10) generated after the solvent recovery and the discharge flow (B4') generated after condensation separation are passed through the degassing unit 660 to separate _{COx and O 2.}

The discharge flow (B11') generated after the degassing includes COx and O ₂ additionally separated from the degassing unit 660, and may be introduced into the condensation system to be recondensed and separated from the condensation separation unit 630, and the Another discharge stream (B4") generated after degassing may include crude hydrocarbons containing n-butane, butene and butadiene, high boiling point substances, etc. excluding _{COx and O 2 additionally separated from the degassing unit 660} , It is introduced into the high boiling point removal unit 680 to separate the high boiling point material.

The discharge stream (B4"') generated after the high boiling point is removed may contain n-butane from which the high boiling point material has been removed, and crude hydrocarbons including butene and butadiene, and pass through the purification unit 640 to separate butadiene. I can.

The discharge stream (B7) generated after the purification may contain an abundant amount of remaining n-butane, and a recycle flow introduced into the oxidative dehydrogenation reaction unit 610 is formed. In another discharge stream (B8) generated after the purification, butadiene is separated from the purification unit 640 and the remaining butene may be included, and the recycle that is mixed with raw material butene and introduced into the oxidative dehydrogenation reaction unit 610 Flow can be formed.

As an example of the manufacturing apparatus used in the manufacturing method, referring to FIG. 2 below, butadiene is included by oxidative dehydrogenation of a reaction raw material including _{butene, oxygen (O 2 ), steam, and dilute gas (butane).} An oxidative dehydrogenation reaction unit 210 to obtain an oxidative dehydrogenation reaction product; A cooling separation unit 220 for separating water from the oxidative dehydrogenation reaction product including the butadiene; A condensation separation unit 230 for condensing hydrocarbons from the oxidative dehydrogenation reaction product from which the water is separated; An absorption separation unit 250 for recovering the entire hydrocarbons in the presence of a non-flammable diluent gas from an oxidation dehydrogenation reaction product including hydrocarbons not condensed in the condensation separation unit 230; Including, a purification unit 240 for separating butadiene from n-butane condensed in the condensation and separation unit 230, butadiene from crude hydrocarbons including butene and butadiene; and n excluding butadiene separated by the purification unit 240 -The discharge stream (B7) containing butane has a configuration that is re-introduced to the oxidation dehydrogenation reaction unit (210).

The discharge stream B6 containing the crude hydrocarbon containing n-butane, butene and butadiene recovered in the presence of a non-flammable diluent gas from the absorption and separation unit 250 is configured to be supplied to the purification unit 240.

The gas containing n-butane excluding butadiene separated by the purification unit 240 is configured to have an exhaust flow B7 that is re-introduced to the oxidative dehydrogenation reaction unit 210. The butadiene is separated from the purification unit 240 and the discharge stream B8 containing the remaining butene is configured to be mixed with the raw material butene and re-introduced into the oxidative dehydrogenation reaction unit 210.

The non-flammable dilution gas may be, for example, nitrogen gas (N ₂ ), argon, helium, or carbon dioxide (CO ₂ ), preferably nitrogen gas.

As an example of another manufacturing apparatus, referring to FIG. 3 below, oxidative dehydrogenation including butadiene by oxidative dehydrogenation reaction of a reaction raw material including _{butene, oxygen (O 2 ), steam and diluent gas (butane)} An oxidative dehydrogenation reaction unit 310 for obtaining a reaction product; A cooling separation unit 320 for separating water from the oxidative dehydrogenation reaction product including the butadiene; A condensation separation unit 330 for condensing hydrocarbons from the oxidative dehydrogenation reaction product from which the water is separated; An absorption separation unit 350 for recovering the entire hydrocarbons in the presence of a non-combustible diluent gas from an oxidation dehydrogenation reaction product including hydrocarbons not condensed in the condensation separation unit 330; The discharge stream (B6') containing hydrocarbons including n-butane, butene and butadiene recovered from the absorption and separation unit 350 is configured to be supplied to the solvent recovery unit 370 for recovering the solvent, and the The discharge stream B9 including the solvent recovered from the solvent recovery unit 370 is configured to be recycled to the absorption and separation unit 350.

The discharge stream (B4') containing hydrocarbons including n-butane, butene and butadiene condensed in the condensation separation unit 330, and n-butane and butene from which the solvent is removed from the solvent recovery unit 370 In the discharge stream (B10) containing hydrocarbons including and butadiene, a degassing unit 360 for separating hydrocarbons including _{COx, O 2, n-butane, butene and butadiene, etc.;} desirable.

_{The exhaust stream B11 containing COx and O 2} separated by the degassing unit 360 is configured to circulate to the absorption and separation unit 350.

The discharge stream (B4") including crude hydrocarbons including n-butane, butene and butadiene excluding _{COx and O 2} separated by the degassing unit 360 is configured to be supplied to the purification unit 340.

The discharge stream (B7) including the purification unit 340 for separating the butadiene and containing n-butane excluding the butadiene separated by the purification unit 340 is reconstituted to the oxidative dehydrogenation reaction unit 310 It is configured to be put in. The butadiene is separated from the purification unit 340 and the discharge stream B8 containing the remaining butene is configured to be re-introduced to the oxidation dehydrogenation reaction unit 310.

The non-flammable dilution gas may be, for example, nitrogen gas (N ₂ ), argon, helium, or carbon dioxide (CO ₂ ), preferably nitrogen gas.

As an example of another manufacturing apparatus, referring to FIG. 4 below, oxidative dehydrogenation including butadiene by oxidative dehydrogenation of a reaction raw material including _{butene, oxygen (O 2 ), steam and diluent gas (butane)} An oxidative dehydrogenation reaction unit 410 to obtain a reaction product; A cooling separation unit 420 for separating water from the oxidative dehydrogenation reaction product including the butadiene; A condensation separation unit 430 for condensing hydrocarbons from the oxidative dehydrogenation reaction product from which the water is separated; An absorption separation unit 450 for recovering the entire hydrocarbons in the presence of a non-flammable diluent gas from an oxidation dehydrogenation reaction product including hydrocarbons not condensed in the condensation separation unit 430; The discharge stream (B6') containing hydrocarbons including n-butane, butene and butadiene recovered from the absorption and separation unit 450 is configured to be supplied to the solvent recovery unit 470 for recovering the solvent, and the solvent The discharge stream B9 including the solvent recovered from the recovery unit 470 is configured to be recycled to the absorption and separation unit 450.

The discharge stream (B4') consisting of hydrocarbons including n-butane, butene and butadiene condensed in the condensation separation unit 430, and n-butane and butene from which the solvent is removed from the solvent recovery unit 470 In the discharge stream (B10) composed of hydrocarbons including butadiene, it is preferable to include a degassing unit 460 for separating hydrocarbons including _{COx, O 2, n-butane, butene and butadiene.}

_{The exhaust stream B11 containing COx and O 2} separated by the degassing unit 460 is configured to circulate to the absorption and separation unit 450.

The discharge stream (B4") containing crude hydrocarbons including n-butane, butene and butadiene, and high-boiling substances excluding _{COx and O 2} separated by the degassing unit 460 is a high-boiling agent to separate high-boiling substances. The discharge stream (B4"') containing crude hydrocarbons including n-butane, butene and butadiene separated from the high boiling point removal unit 480 is supplied to the refining unit.

Including a purification unit 440 for separating the butadiene, and the discharge flow B7 containing n-butane excluding butadiene separated by the purification unit 440 is directed to the oxidative dehydrogenation reaction unit 410 It is configured to be reintroduced. The butadiene is separated from the purification unit 440 and the discharge stream B8 containing the remaining butene is configured to be re-introduced into the oxidation dehydrogenation reaction unit 410.

The non-flammable dilution gas may be, for example, nitrogen gas (N ₂ ), argon, helium, or carbon dioxide (CO ₂ ), preferably nitrogen gas.

The high boiling point substance is, for example, an aromatic hydrocarbon such as furan, aldehyde, acetic acid, benzene, or phenol, or styrene.

As an example of another manufacturing apparatus, referring to FIG. 5 below, oxidative dehydrogenation including butadiene by oxidative dehydrogenation reaction of a reaction raw material including _{butene, oxygen (O 2 ), steam and diluent gas (butane)} An oxidative dehydrogenation reaction unit 510 to obtain a reaction product; A cooling separation unit 520 for separating water from the oxidative dehydrogenation reaction product including the butadiene; A condensation separation unit 530 for condensing hydrocarbons from the oxidative dehydrogenation reaction product from which the water is separated; An absorption separation unit 550 for recovering the entire hydrocarbons in the presence of a non-flammable diluent gas from an oxidation dehydrogenation reaction product including hydrocarbons not condensed in the condensation separation unit 530; The discharge stream (B6') containing hydrocarbons including n-butane, butene and butadiene recovered from the absorption and separation unit 550 is configured to be supplied to the solvent recovery unit 570 for recovering the solvent, and the The discharge stream B9 including the solvent recovered from the solvent recovery unit 570 is configured to be recycled to the absorption and separation unit 550.

An exhaust stream (B4') containing hydrocarbons including n-butane, butene and butadiene condensed in the condensation separation unit 530, and n-butane from which the solvent is removed from the solvent recovery water 570, In the discharge stream (B10) containing hydrocarbons including butene and butadiene, COx, O ₂ and a degassing unit 560 for separating hydrocarbons including n-butane, butene and butadiene, etc.; It is desirable.

The discharge stream (B4") including crude hydrocarbons including n-butane, butene and butadiene excluding _{COx and O 2} separated by the degassing unit 560 is configured to be supplied to the refining unit 340, and the _{The discharge stream (B11') including COx and O 2} separated by the degassing unit 560 flows into the condensation system and is configured to be recycled to the condensation separation unit 530.

Unless otherwise specified, the condensation system refers to a system including a compressor 531, a heat exchanger 532, and a condensation separator 530.

Including a purification unit 540 separating the butadiene; and the discharge flow (B7) containing n-butane excluding butadiene separated from the purification unit 540, to the oxidation dehydrogenation reaction unit 510 It is configured to be reintroduced. The butadiene is separated from the purification unit 540 and the discharge stream B8 containing the remaining butene is configured to be re-introduced into the oxidation dehydrogenation reaction unit 210 by merging with the raw material butene.

The non-flammable dilution gas may be, for example, nitrogen gas (N ₂ ), argon, helium, or carbon dioxide (CO ₂ ), preferably nitrogen gas.

Referring to FIG. 6 below as an example of another manufacturing apparatus, oxidative dehydrogenation including butadiene by oxidative dehydrogenation reaction of a reaction raw material including _{butene, oxygen (O 2 ), steam and diluent gas (butane)} An oxidative dehydrogenation reaction unit 610 to obtain a reaction product; A cooling separation unit 620 for separating water from the oxidative dehydrogenation reaction product including the butadiene; A condensation separator 630 for condensing hydrocarbons from the oxidative dehydrogenation reaction product from which the water is separated; An absorption separation unit 650 for recovering the entire hydrocarbons in the presence of a non-combustible diluent gas from an oxidation dehydrogenation reaction product including hydrocarbons not condensed in the condensation separation unit 630; The discharge stream (B6') containing hydrocarbons including n-butane, butene and butadiene recovered from the absorption and separation unit 650 is configured to be supplied to the solvent recovery unit 670 for recovering the solvent, and the solvent The discharge stream B9 including the solvent recovered from the recovery unit 670 is configured to be recycled to the absorption and separation unit 650.

The discharge stream (B4') consisting of hydrocarbons including n-butane, butene and butadiene condensed in the condensation separation unit 630, and n-butane and butene from which the solvent is removed from the solvent recovery unit 670 In the discharge stream (B10) composed of hydrocarbons including butadiene, it is preferable to include a degassing unit 660 for separating hydrocarbons including _{COx, O 2 and n-butane, butene and butadiene.}

_{The discharge stream (B11') containing COx and O 2} separated by the degassing unit 660 flows into the condensation system and is circulated to the condensation separation unit 630.

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

The discharge stream (B4") containing crude hydrocarbons including n-butane, butene and butadiene, and high-boiling substances excluding _{COx and O 2} separated by the degassing unit 660 is a high-boiling agent to separate high-boiling substances. The discharge stream (B4"') containing crude hydrocarbons including n-butane, butene and butadiene separated from the high boiling point removal unit 680 is supplied to the refining unit.

Including a purification unit 640 separating the butadiene; and the discharge flow (B7) containing n-butane excluding butadiene separated from the purification unit 640, to the oxidative dehydrogenation reaction unit 610 It is configured to be reintroduced. The butadiene is separated from the purification unit 640 and the discharge stream B8 containing the remaining butene is configured to be re-introduced to the oxidation dehydrogenation reaction unit 610.

The non-flammable dilution gas may be, for example, nitrogen gas (N ₂ ), argon, helium, or carbon dioxide (CO ₂ ), preferably nitrogen gas.

The high boiling point substance is, for example, an aromatic hydrocarbon such as furan, aldehyde, acetic acid, benzene, or phenol, or styrene.

_{The heat generated by incineration of the COx and O 2} separated in the presence of a non-flammable diluent gas in the absorption and separation unit 250, 350, 450, 550, 650 and a non-flammable diluent gas is converted into a raw material heat up, 370, 470, 570, 670), or the absorption and separation unit 250, 350, 450, 550, 650 and the oxidative dehydrogenation reaction unit 210 to be recycled in the purification unit 240, 340, 440, 540, 640 , 310, 410, 510, 610), or between the absorption separation unit (250, 350, 450, 550, 650) and the condensation separation unit (240, 340, 440, 540, 640), or the absorption separation unit A heat exchange means between (250, 350, 450, 550, 650) and the oxidation dehydrogenation reaction unit (210, 310, 410, 510, 610) and the condensation separation unit (240, 340, 440, 540, 640) It can be provided.

The use of the butadiene manufacturing method and the manufacturing apparatus used therein described so far can compensate for the disadvantages of the manufacturing method using nitrogen as a dilution gas in a conventional butadiene manufacturing process and increase the treatment effect, and reduce energy consumption in the processing process. Energy efficiency can be maximized by minimizing it. In addition, the method for producing butadiene of the present invention can be used directly for purification/manufacturing of materials for various purposes (ACN, NMP, DMF, etc.), so it can be applied to various processes.

Hereinafter, a preferred embodiment is presented to aid in the understanding of the present invention, but it is obvious to those skilled in the art that various changes and modifications are possible within the scope of the present invention and the scope of the technical idea, but the following examples are only illustrative of the present invention, It is natural that such modifications and modifications fall within the scope of the appended claims.

[ Example ]

Example One

Using the apparatus of FIG. 2 below, butene:oxygen = 1:0.9, butene:water vapor = 1:5, butene:butane under a ferritic catalyst using raffinate-3 having the composition shown in Table 1 as a raw material for the oxidation carbonization reaction = 1: After the reaction product having a molar ratio of 1:4 was subjected to oxidative dehydrogenation, water was removed from the cooling separation unit, and then condensation separation and absorption separation steps were performed to obtain crude hydrocarbons as a raw material of the purification unit.

The oxidative dehydrogenation reaction product from which water was removed from the cooling separator was put into a condensation separator, pressurized by a two-stage compressor, and hydrocarbons were condensed at 40°C using cooling water. Condensation conditions prevented the composition of the gaseous phase generated in the condensation separation unit from entering the explosive area, and toluene was used to absorb the entire hydrocarbons in the absorption and separation unit in order to minimize the loss of effective hydrocarbons existing in the gas phase after condensation separation. At this time, nitrogen was added to the absorption and separation unit so that the composition of the gaseous phase generated from the absorption and separation did not enter the explosive area. The entire absorption of hydrocarbons using toluene in the presence of nitrogen in the absorption and separation section eliminated the possibility of explosion in the main gaseous stream in the process, thereby ensuring safety, and obtaining crude hydrocarbons, which are raw materials for the purification section, with a 99% butadiene recovery rate.

At this time, the discharge flow of the oxidative dehydrogenation reaction unit is measured by gas chromatography, and the discharge flows of the cooling separation unit, condensation separation unit, and absorption separation unit (B1, B2, B3, B3-1, B5, B4+B6) The composition in was calculated with a process simulator (AspenPlus) and shown in Table 2 below.

In addition, the solvent and amount used in the absorption and separation unit are shown in Table 5, and the oxygen concentration is shown in Table 6.

Comparative example One

In Example 1, the compressed discharge temperature in the condensation separation unit was set to 80°C, pressurized by a two-stage compressor, and hydrocarbons were condensed to 40°C using cooling water. In order to minimize the loss of effective hydrocarbons existing in the gas phase of the condensation separation unit, the absorption separation unit was carried out in the same manner as in Example except that the entire hydrocarbons were absorbed using toluene without _{N 2, which is a non-flammable diluent gas.} In %, crude hydrocarbons as raw materials for the refining unit were obtained.

However, safety was not secured as the main gaseous flow in the process entered the explosive zone.

At this time, the discharge flow of the oxidation dehydrogenation reaction unit is measured by gas chromatography, and the composition in the discharge flows (B1, B2, B3, B5, B4 + B6) of the cooling separation unit, the condensation separation unit, and the absorption separation unit is Calculated with a process simulator (AspenPlus) and shown in Table 3 below.

Comparative example 2

Using the apparatus of FIG. 1 below, a reaction raw material having a molar ratio of butene:oxygen=1:0.96, butene:steam=1:5, butene:nitrogen=1:4 was oxidized under a waste lite catalyst using nitrogen as a dilution gas. Dehydrogenation yielded butadiene. After removing the water in the reaction product in the cooling separation unit, the final product was obtained through an absorption separation unit and a purification unit. By using nitrogen as the diluting gas, the possibility of explosion in the main gaseous stream in the process was eliminated to ensure safety, and crude hydrocarbons, which are raw materials for the refinery, were obtained with a 99% butadiene recovery rate.

In each process of FIG. 1, the main flow including the absorption and separation unit 130 is calculated by a process simulator (AspenPlus) and is shown in Table 4 below, and the amount of solvent used in the absorption and separation unit and the energy consumption required for recovery of the used solvent are shown. It is shown in 5.

Table 5 shows the amount of solvent used in the absorption and separation unit of Example 1 and Comparative Examples 1 and 2 and the amount of energy required for recovery of the used solvent, and the oxygen concentration in the main stream and the explosive area in the absorption and separation unit are shown in Table 6. .

Furtherance mole% wt% 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

Example Oxidative dehydrogenation reaction unit 210 and
Cooling separation unit 220 Condensation separation unit 230 and absorption separation unit 250 Pressure (kg/cm ² g) 1.0 0.5 0.1 5.0 5.0 4.4 3.0 Temperature(℃) 350 350 35 40 35 57 40 Mass flow
(kg/hr) Reactant B1 B2 B3 B3-1 B5 B4+B6 Oxygen 12,203 1,945 1,945 1,915 1,915 1,945 - nitrogen - - - - 10,000 10,000 - COx - 4,080 4,079 3,687 3,687 4,078 - water 38,167 46,375 1,250 124 124 132 - light
Gas flow* - 3 3 3 3 3 - Carbonyl and
Aldehydes - 73 68 13 13 8 59 1-butene - 210 210 40 40 4 206 1,3-butadiene - 18,755 18,755 3,672 3,672 188 18,567 n-butane 98,512 98,512 98,512 16,371 16,371 1,626 96,886 Acetylenes - 23 23 5 5 0 23 Trans-2-butene 14,264 1,787 1,787 294 294 8 1,779 Cis-2-butene 9,510 610 610 95 95 2 608 High boiling point substance** - 283 147 3 3 107 29 toluene - - - - - 1,392 0 DMF - - - - - - - Sum 172,656 172,656 127,388 26,220 36,220 19,492 118,158

Oxidative dehydrogenation reaction unit 210 and
Cooling separation unit 220 Condensation separation unit 230 and
Absorption separation unit 250 Pressure (kg/cm ² g) 1.0 0.5 0.1 9.7 7.0 3.0 Temperature(℃) 350 350 35 40 78 40 Mass flow
(kg/hr) Reactant B1 B2 B3 B5 B4+B6 Oxygen 12,203 1,945 1,945 1,828 1,945 - nitrogen - - - - - - COx - 4,080 4,079 2,929 4,077 - water 38,167 46,375 1,250 32 47 - Light gas flow* - 3 3 2 3 - Carbonyl and
Aldehydes - 73 68 4 7 59 1-butene - 210 210 11 3 207 1,3-butadiene - 18,755 18,755 981 188 18,567 n-butane 98,512 98,512 98,512 4,302 1,232 97,280 Acetylenes - 23 23 2 0 23 Trans-2-butene 14,264 1,787 1,787 77 10 1,777 Cis-2-butene 9,510 610 610 25 2 608 High boiling point substance** - 283 147 One 92 38 toluene - - - - 628 0 DMF - - - - - - Sum 172,656 172,656 127,388 10,193 8,233 118,558

* Light gas streams: Substances with a lower boiling point than C4 types excluding COx and O ₂

** High-boiling substances: aromatic hydrocarbons such as benzene, styrene, and phenol, butadiene dimers, acetopinone, benzopinone or anthrequinone

Oxidative dehydrogenation reaction unit 110 and
Cooling separation unit (120) Absorption separation unit 130 Pressure (kg/cm ² g) 1.0 1.0 0.7 3.4 3.0 Temperature(℃) 350 350 35 44 33 Mass flow
(kg/hr) Reactant B1 B2 B3 B4 Oxygen 13,013 2,757 2,757 2,757 - nitrogen 42,855 42,855 42,855 42,855 - COx - 4,078 4,078 4,078 - water 38,156 46,363 1,250 350 306 Light gas flow
(COx, O _2, etc.) - 3 3 3 - Carbonyl and
Aldehydes - 73 68 7 60 1-butene - 209 209 5 205 1,3-butadiene - 18,750 18,750 188 18,562 n-butane 9,575 9,575 9,575 253 9,321 Acetylenes - 23 23 0 23 Trans-2-butene 14,260 1,786 1,786 10 1,776 Cis-2-butene 9,507 610 610 2 607 High boiling point substances - 283 147 91 42 toluene - - - 3,582 0 DMF - - - - - Sum 127,366 127,366 82,111 54,182 30,903

Example 1 Comparative Example 1 Comparative Example 2 In the absorption and separation part
Solvent usage (ton/hr) 154 51 358 When recovering the solvent in the absorption and separation part
Energy consumption (Gcal/hr) 21.7 14.7 27.6

Oxygen concentration in the absorption and separation section (Mol%) Example 1 Comparative Example 1 Comparative Example 2 B2 - - 3.7 B3 11.7 25.6 4.8 B3-1 6.9 - - B5 10.7 31.6 -

_{As shown in Tables 2 to 6, hydrocarbons including COx, O 2} , N ₂ and n-butane, butene and butadiene in the presence of nitrogen gas as a non-flammable diluent gas in the absorption and separation unit using butane instead of nitrogen as a diluting gas. In the case of separating, it was confirmed that safety in the process can be secured. In addition, Example 1 using butane instead of nitrogen as the diluent gas according to the present invention, compared to Comparative Example 2 using nitrogen, the amount of solvent used in the absorption and separation unit was significantly reduced, thereby reducing energy consumption, thereby economically producing high purity butadiene. Could be manufactured.

110, 210, 310, 410, 510, 610: oxidative dehydrogenation reaction section
130, 250, 350, 450, 550, 650: absorption and separation unit
120, 220, 320, 420, 520, 620: cooling separator
230, 330, 430, 530, 630: condensation separation unit
140, 240, 340, 440, 540, 640: refining unit
360, 460, 560, 660: degassing unit
370, 470, 570, 670: solvent recovery unit
480, 680: high boiling point removal unit
531, 631: compressor
532, 632: heat exchanger

Claims (23)

Passing a reaction raw material containing butene, oxygen (O ₂ ), steam, and a diluted gas through an oxidation dehydrogenation reaction unit to generate an oxidative dehydrogenation reaction product containing butadiene; and
Separating water while passing the oxidative dehydrogenation reaction product including the butadiene through a cooling separation unit,
Condensing hydrocarbons while passing the oxidative dehydrogenation reaction product from which the water is separated through a condensation separator,
Recovering the entire hydrocarbons in the presence of a non-flammable diluent gas while passing an oxidation dehydrogenation reaction product including hydrocarbons that are not condensed in the condensation separation unit through an absorption separation unit,
Separating butadiene while passing an oxidative dehydrogenation reaction product including hydrocarbons including n-butane, butene and butadiene condensed in the condensation separation unit through a purification unit,
Gas containing n-butane and butene, excluding butadiene separated by the purification unit, is re-introduced into the oxidation dehydrogenation reaction unit, and the diluting gas is butane. The method of claim 1,
_{A method for producing butadiene, characterized in that oxygen (O 2} ) contained in the reaction raw material is introduced in the form of a gas having a purity of 90% or more. The method of claim 1,
The reaction conditions in the oxidative dehydrogenation reaction unit are butene: oxygen: water vapor: diluted gas = 1: 0.5 to 3: 0.1 to 20: a method for producing butadiene, characterized in that the molar ratio of 0.1 to 20. The method of claim 1,
The condensation separation is a single compression structure of one stage, a multi-stage compression structure of 2 to 10 stages, or a multi-stage compression of 1 stage to 2 stages, and the compression discharge temperature is 50 to 250°C. The method of claim 1,
The refrigerant used in the condensation separation is 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 solution of propylene glycol having a concentration of 30 to 100% by weight, and a propylene-based solvent. Method for producing butadiene, characterized in that. The method of claim 1,
_{The step of separating butadiene by passing a crude hydrocarbon containing n-butane, butene and butadiene excluding COx and O 2} separated in the absorption and separation unit through a purification unit or introducing it to a solvent recovery unit to absorb the solvent. Method for producing butadiene.
The method of claim 1,
_{Separating COx and O 2} while passing an oxidative dehydrogenation reaction product including hydrocarbons not condensed in the condensation separation unit through an absorption separation unit, and containing n-butane, butene and butadiene condensed in the condensation separation unit The step of separating butadiene while passing the discharge stream containing the hydrocarbons to the refining unit
_{COx and O 2} separated in the presence of non-flammable diluent gas in the absorption and separation unit, n-butane excluding non-combustible diluent gas, butene and the discharge flow including hydrocarbons including butadiene, pass through the solvent recovery unit to recover the solvent, Reintroducing the recovered solvent into the absorption and separation unit,
The method comprising: with the COx and O ₂ separated from the solvent recovery unit, while the hydrocarbons condensed in the condensation separation unit, passing a degassing additional separating COx and O _{2,
Injecting COx and O 2} further separated from the degassing unit into the absorption and separation unit,
The method for producing butadiene, characterized in that comprising the step of introducing a hydrocarbon containing n-butane, butene and butadiene, excluding _{COx and O 2} separated by the degassing unit, into the purification unit. The method of claim 1,
_{Separating COx and O 2} while passing an oxidation dehydrogenation reaction product including hydrocarbons that are not condensed in the condensation separation unit through an absorption separation unit,
The step of separating butadiene while passing the discharge stream containing hydrocarbons including n-butane, butene and butadiene condensed in the condensation separation unit through the purification unit,
_{COx and O 2} separated in the presence of non-flammable diluent gas in the absorption and separation unit, hydrocarbons including n-butane, butene and butadiene excluding non-combustible diluent gas, pass through a solvent recovery unit to recover the solvent, and collect the recovered solvent. Reintroducing into the absorption separation unit,
The method comprising the hydrocarbons condensed in the COx and O ₂ and the condensation separation section separated from the solvent recovery unit, it was passed through a degassing additional separating COx and O _2,
Separating crude hydrocarbons while passing hydrocarbons containing n-butane, butene and butadiene excluding _{COx and O 2} further separated in the degassing unit through a high boiling point removal unit, and
The method for producing butadiene, characterized in that the step of introducing the crude hydrocarbon separated in the high boiling point removal unit into the purification unit. The method of claim 1,
_{Separating COx and O 2} while passing an oxidative dehydrogenation reaction product including hydrocarbons not condensed in the condensation separation unit through an absorption separation unit, and containing n-butane, butene and butadiene condensed in the condensation separation unit The step of separating butadiene while passing the hydrocarbons through the purification unit
_{Hydrocarbons including COx, O 2} and n-butane, butene and butadiene excluding non-combustible diluent gas separated in the presence of non-flammable diluent gas in the absorption and separation unit pass through a solvent recovery unit to recover the solvent, and the recovered Reintroducing a solvent into the absorption and separation unit,
The method comprising: with the COx and O ₂ separated from the solvent recovery unit, while the hydrocarbons condensed in the condensation separation unit, passing a degassing additional separating COx and O _2,
Injecting the additionally separated COx and O ₂ in the degassing unit into the condensation system,
A method for producing butadiene, comprising the step of introducing a crude hydrocarbon containing n-butane, butene and butadiene, excluding _{COx and O 2} further separated in the degassing unit into the refining unit. The method of claim 1,
_{Separating COx and O 2} while passing an oxidative dehydrogenation reaction product including hydrocarbons not condensed in the condensation separation unit through an absorption separation unit, and containing n-butane, butene and butadiene condensed in the condensation separation unit The step of separating butadiene while passing the crude hydrocarbon through the purification unit
_{The discharge flow including COx and O 2} separated in the presence of non-flammable diluent gas in the absorption and separation unit and hydrocarbons including n-butane, butene and butadiene excluding non-combustible diluent gas passes through the solvent recovery unit to recover the solvent, and , Reintroducing the recovered solvent to the absorption and separation unit,
The method comprising: a discharge flow containing the COx and O _2, and the hydrocarbons condensed in the condensation separation section separated from the solvent recovery unit, it was passed through a degassing additional separating COx and O _2,
Injecting the additionally separated COx and O ₂ in the degassing unit into the condensation system,
Separating crude hydrocarbons while passing hydrocarbons containing n-butane, butene and butadiene excluding _{COx and O 2} further separated in the degassing unit through a high boiling point removal unit, and
The method for producing butadiene, characterized in that the step of introducing the crude hydrocarbon separated in the high boiling point removal unit into the purification unit. The method of claim 1,
The non-flammable diluent gas is nitrogen gas (N ₂ ), argon, helium, or carbon dioxide (CO ₂ ). The method of claim 1,
The oxidative dehydrogenation reaction unit contains butene, oxygen (O ₂ ), steam, and a gas containing n-butane that is re-introduced to the oxidation dehydrogenation reaction unit as a residue from which butadiene is separated from the purification unit. A method for producing butadiene, characterized in that it is driven under isothermal or adiabatic conditions at a reaction temperature of 150 to 650°C using a ferritic catalyst as a reaction raw material. The method of claim 1,
The cooling separating unit is a method for producing butadiene, characterized in that driven by a direct cooling method (quencher) of rapid cooling or an indirect cooling method. The method of claim 1,
The absorption separating unit is a method for producing butadiene, characterized in that it is driven in an absorption method using a solvent for separating _{COx and O 2} in the presence of a non-flammable diluent gas. The method of claim 1,
The method for producing butadiene, wherein the non-flammable diluent gas is introduced while transporting an oxidation dehydrogenation reaction product including hydrocarbons not condensed in the condensation separation unit to the absorption separation unit. The method according to any one of claims 6 to 10,
The method for producing butadiene, characterized in that the degassing unit or the solvent recovery unit is driven by stripping or degassing using a general column. An oxidative dehydrogenation reaction unit for obtaining an oxidative dehydrogenation reaction product including butadiene by subjecting a reaction raw material including butene, oxygen (O _{2 ), steam, and a diluted gas to an oxidative dehydrogenation reaction;}
A cooling separation unit for separating water from the oxidative dehydrogenation reaction product including the butadiene;
A condensation separator for condensing hydrocarbons from the oxidative dehydrogenation reaction product from which the water is separated;
Separating the oxidative dehydrogenation reaction product including hydrocarbons that are not condensed in the condensation separation unit into COx, O ₂ and non-combustible diluent gas in the presence of non-combustible diluent gas, and hydrocarbons including n-butane, butene and butadiene Absorption separation unit; And
Including; a purification unit for separating butadiene from the crude hydrocarbon condensed in the condensation separation unit,
Gas containing n-butane and butene, excluding butadiene separated by the purification unit, is re-introduced into the oxidation dehydrogenation reaction unit, and the dilution gas is butane. The method of claim 17,
_{Butadiene, characterized in that it comprises an exhaust stream supplied to the refining unit of COx and O 2} separated in the absorption and separation unit in the presence of non-combustible diluent gas, n-butane excluding non-combustible diluent gas, butene and crude hydrocarbons including butadiene. Manufacturing device. The method of claim 17,
A solvent recovery unit for recovering a solvent from an exhaust stream containing hydrocarbons including _{COx, O 2} and n-butane, butene and butadiene excluding non-flammable diluent gas separated by the absorption and separation unit in the presence of a non-flammable diluent gas; And a discharge flow for re-introducing the solvent recovered from the solvent recovery unit into the absorption and separation unit. The method of claim 19,
Butadiene, characterized in that it further comprises a degassing unit for separating _{COx, O 2} and hydrocarbons in the discharge stream containing hydrocarbons including n-butane, butene and butadiene excluding the solvent recovered from the solvent recovery unit. Manufacturing device. The method of claim 20,
The apparatus for producing butadiene further comprises a; discharge flow through _{which COx and O 2} separated by the degassing unit are introduced into the absorption and separation unit. The method of claim 20,
An apparatus for producing butadiene further comprising a; discharge flow through _{which COx and O 2} separated by the degassing unit are introduced into the condensation system. The method of claim 20,
A high boiling point removal unit for separating crude hydrocarbons from the discharge stream containing hydrocarbons including n-butane, butene and butadiene separated by the degassing unit; And
An exhaust stream in which the crude hydrocarbon separated from the high boiling point removal unit is introduced into the refining unit; Butadiene production apparatus, characterized in that it further comprises.

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