WO2015186915A1 - 산화탈수소화 반응을 통한 부타디엔의 제조방법 - Google Patents
산화탈수소화 반응을 통한 부타디엔의 제조방법 Download PDFInfo
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- WO2015186915A1 WO2015186915A1 PCT/KR2015/004928 KR2015004928W WO2015186915A1 WO 2015186915 A1 WO2015186915 A1 WO 2015186915A1 KR 2015004928 W KR2015004928 W KR 2015004928W WO 2015186915 A1 WO2015186915 A1 WO 2015186915A1
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- butadiene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/12—Alkadienes
- C07C11/16—Alkadienes with four carbon atoms
- C07C11/167—1, 3-Butadiene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
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- the present invention relates to a method for producing butadiene through oxidative dehydrogenation.
- Butadiene is used as an intermediate of many petrochemical products in the petrochemical market and is one of the most important basic oils in the petrochemical market, and its demand and value are gradually increasing.
- butadiene production method is extracted from C4 fraction through naphtha cracking, direct dehydrogenation of n-butene, oxidative dehydrogenation of n-butene (n-butene) , ODH)) reactions.
- the naphtha cracking process which is responsible for more than 90% of butadiene in the market, consumes a lot of energy due to high reaction temperature and is not a sole process for butadiene production. The problem is that it is produced in surplus.
- the manufacturing method through the direct dehydrogenation of normal-butene is not only thermodynamically disadvantageous, but also suitable for the commercialization process for producing butadiene due to the endothermic reaction requiring high temperature and low pressure to produce high yield of butadiene. not.
- a method for preparing butadiene through oxidative dehydrogenation reaction (ODH) of normal-butene is using a reaction of removing two hydrogens from normal-butene using oxygen as a reactant to generate butadiene, which is stable as a product. Since water is produced, it is very thermodynamically advantageous, and unlike direct dehydrogenation, it is exothermic and thus high yield of butadiene can be obtained at a lower reaction temperature than direct dehydrogenation. Therefore, the method for producing butadiene through the oxidative dehydrogenation of normal-butene may be an effective production process that can meet the growing demand for butadiene.
- the method of preparing butadiene by oxidative dehydrogenation of the normal-butene may reduce the risk of explosion of the reactants and at the same time, in addition to the reaction materials (normal-butene and oxygen) to prevent coking of the catalyst and to remove the heat of reaction. Inject nitrogen, steam, etc. Therefore, butadiene as a main product, carbon monoxide, carbon dioxide, and the like by-products are generated secondary, and carbon monoxide, etc., in the by-products should be separated and discharged so that continuous accumulation does not occur in the process.
- the effective components such as oxygen, unreacted raw material (normal-butene), and butadiene produced are discharged together outside the system.
- air is generally used as an input source of oxygen (O 2 ) and nitrogen (N 2 ) in an oxidative dehydrogenation reaction, in which case nitrogen, oxygen, unreacted raw materials and butadiene are discharged.
- oxygen oxygen
- N 2 nitrogen
- the present invention has been made in order to solve the problems of the prior art as described above, by easily adding the oxygen (O 2 ) and nitrogen (N 2 ) included in the reaction raw material stream to each other easily the ratio of the oxygen and nitrogen It is an object of the present invention to provide a method for producing butadiene through an oxidative dehydrogenation reaction that can minimize the amount of active ingredients discharged by adjusting.
- the present invention is to react the oxidative dehydrogenation reaction by introducing a reaction raw material stream containing C4 fraction, steam, oxygen (O 2 ) and nitrogen (N 2 ) into the reactor filled with a catalyst Advancing (step a); Separating the C4 mixture comprising butadiene obtained from the reactor and a light gas (step b); And purifying the C4 mixture comprising the butadiene (step c),
- the first fraction stream provides a process for producing butadiene through an oxidative dehydrogenation reaction comprising at least one of nitrogen and carbon dioxide.
- the production method according to the present invention can easily control the input ratio of oxygen and nitrogen contained in the reaction raw material stream, thereby minimizing the amount of active ingredients such as butadiene contained in the second fraction stream discharged to the outside of the system The loss of active ingredient can be reduced.
- the raw material cost is reduced, productivity is improved, and the amount of incineration of the purge discharged to the outside of the system is reduced, thereby improving economic efficiency of the process.
- Figure 1 is a schematic diagram showing the manufacturing process of butadiene using a conventional general oxidative dehydrogenation reaction according to an embodiment of the present invention.
- Figure 2 shows a schematic diagram of a butadiene production process using an oxidative dehydrogenation reaction through a method of injecting oxygen and nitrogen into independent pure gas according to an embodiment of the present invention.
- the term "light gas” as used throughout this specification, including claims and abstracts, refers to nitrogen, oxygen, water vapor, carbon monoxide or carbon dioxide in the reaction products produced through oxidative dehydrogenation reactions. It may mean a gas component containing.
- active ingredient may mean a component effective for the butadiene production reaction, such as nitrogen, oxygen, unreacted raw materials or butadiene.
- the present invention is to prepare the butadiene through the oxidative dehydrogenation reaction that can reduce the loss of the active ingredient, such as butadiene discharged to the outside after the reaction by controlling the ratio of oxygen (O 2 ) and nitrogen (N 2 ) in the reaction raw material stream Provide a method.
- a method for producing butadiene through an oxidative dehydrogenation reaction includes a reaction raw material input line 1, a reactor 10, a reaction product transfer line 2, a gas separator 20, and an internal circulation line. (3), through a manufacturing apparatus comprising a discharge line 4, a separate C4 mixture transfer line 5, a refining apparatus 30 and a purified butadiene discharge line 6.
- the reaction raw material is introduced into the reactor 10 through the reaction raw material input line 1 used for the production of butadiene, and a reaction product is obtained through an oxidative dehydrogenation reaction in the reactor 10.
- the reaction product obtained enters the gas separator 20 via the reaction product transfer line 2 and is separated into a C4 mixture and a gas product.
- Some of the separated gaseous product e.g. nitrogen
- Discharged is also introduced into the purification apparatus 30 via C4 mixture transfer line 5 and purified to produce butadiene via butadiene discharge line 6.
- oxidative dehydrogenation reaction may proceed, and the oxidative dehydrogenation reaction may be an exothermic reaction, and a main reaction formula may be as in Scheme 1 or 2 below.
- the manufacturing process of butadiene through the oxidative dehydrogenation reaction includes oxygen, nitrogen, steam, etc. to prevent the coking of the catalyst and to remove the heat of reaction while reducing the explosion risk of the reactants.
- a secondary reaction raw material low-boiling and water-soluble by-products such as butadiene as the main product, carbon monoxide (CO), carbon dioxide (CO 2 ), acetylene or carbonyl as by-products, and high-boiling by-products such as phenol and coumarin Side reaction products, including the like, are generated in a secondary manner, and carbon monoxide and the like in the by-products must be separated and discharged so that continuous accumulation does not occur in the process.
- FIG. 1 is a conventional butadiene production method is the oxygen and nitrogen is introduced through the air (air), the air, steam or internal circulation line (4) is introduced to the oxygen concentration in consideration of the explosion range of the reactants It is controlled with some gaseous product re-injected through.
- the mass ratio of oxygen to nitrogen is fixed at 20:78, and the ratio of nitrogen and steam according to the reaction conditions in the reactor 10 is also determined, so that the gas is re-injected to maintain the oxygen concentration in the reactor 10.
- the amount of product can only be determined dependently.
- the concentration of oxygen in the reactor 10 is adjusted by introducing air, the concentration of nitrogen is greatly increased because the mass ratio of nitrogen in the air is high, so the amount of the gas product containing nitrogen that can be re-introduced into the reactor is limited. It must be.
- the amount of gaseous products discarded through the discharge line 4 is greater than the amount of gaseous products that are re-injected, so that a relatively large amount of butadiene, unreacted raw materials, etc. is discarded, butadiene manufacturing process It acts as one of the factors that worsen the economics.
- the production method of the present invention can precisely control the flow rate (mass) of oxygen and nitrogen by injecting oxygen and nitrogen in the form of pure gas in order to improve the problems of the prior art as described above, and more than the amount necessary for the reaction It is characterized in that to prevent excessive inclusion.
- the reaction raw material stream comprising C4 fraction, steam, oxygen (O 2 ) and nitrogen (N 2 )
- introducing a catalyst into the reactor filled with the oxidative dehydrogenation reaction step a); Separating a C4 mixture comprising butadiene obtained from the reactor and a light gas (step b); And purifying the C4 mixture comprising the butadiene (step c).
- the gas product separated in step b) is separated into a first fraction stream and a second fraction stream so that the first fraction stream is reintroduced into the reactor, the second fraction
- the stream is further characterized by the step d) of exiting the system.
- the production method according to the present invention can be carried out the reaction raw material input line (1), oxidative dehydrogenation reaction for introducing the reaction raw material stream containing C4 fraction, steam, oxygen and nitrogen into the reactor Reactor 10, a reaction product transfer line 2 for introducing the reaction product obtained from the reactor into the gas separator, a gas separator 20 for separating the C4 mixture and a light gas from the reaction product, a gas separator
- a manufacturing apparatus comprising a C4 mixture conveying line 5, a refiner 30 and a purified butadiene discharge line 6 for transferring the separated C4 mixture to the refiner Can be done.
- the reactor feed line 1 includes a separate pipeline for introducing each component of the reactor feed stream comprising C4 fraction, steam, oxygen and nitrogen into the reactor 10, or the reactor 10 and It may be to include a plurality of individual pipelines branched from one directly connected pipeline, each component of the reactant stream is fed separately.
- the gas separator 20 is for separating the gas product (light gas) and the C4 mixture containing butadiene from the reaction product introduced through the reaction product transfer line (2), if necessary absorption tower and degassing column It may include at least one of.
- the manufacturing apparatus for performing the manufacturing method according to an embodiment of the present invention is a quenching tower (quenching tower) for cooling the reaction product obtained from the reactor between the reactor 10 and the gas separator 20, etc.
- a quenching device including a compressor, a compressor for compressing the reaction product, and a dehydration device for removing water included in the reaction product may be further included.
- the purification device 30 includes a solvent separation and recovery device including a solvent recovery tower, a high boiling point removal tower, a solvent purification tower, and the like, and a purification tower for purifying high purity butadiene, if necessary, in order to obtain high purity butadiene. It may include.
- Step a is an oxidative dehydrogenation reaction by introducing a reactant stream comprising C4 oil, steam, oxygen (O 2 ) and nitrogen (N 2 ) into a catalyst-filled reactor to produce butadiene from the C4 fraction. Step to proceed.
- the mass ratio of each of the active ingredients (C4 fraction, steam, oxygen and nitrogen) in the reactor may be controlled by the incoming raw material stream and the first fraction stream to be re-introduced later.
- the first fractional stream may include any one or more of nitrogen and carbon dioxide as main components, and may further include unreacted raw materials such as oxygen and steam. That is, the active ingredients (C4 fraction, steam, oxygen and nitrogen) in the reactor may be a mixture of the input from the reaction raw material stream and the input from the first fraction stream, the mass ratio of the active ingredient is the introduced reaction It may be adjusted according to the mass ratio of the active ingredient in the feed stream and the mass ratio of the active ingredient in the first fraction stream.
- the mass ratio of oxygen and nitrogen in the reactor is controlled by the mass ratio of oxygen and nitrogen in the reactant stream and the mass ratio of oxygen and nitrogen in the first fraction stream to be reintroduced, and thus to the mass ratio of oxygen and nitrogen in the incoming reactant stream. Accordingly, the reflow amount of the first fractional stream may be dependent, and as a result, the discharge of the second fractional stream, which will be described later, may also be dependent.
- conventional conventional production methods use oxygen and nitrogen contained in the reaction raw material stream as air, and in this case, the mass ratio of oxygen and nitrogen in the air is fixed at 0.2: 0.78 to perform the oxidative dehydrogenation reaction.
- the mass ratio of oxygen, the main active ingredient, to an appropriate condition the mass ratio of nitrogen, a secondary active ingredient, increases more than the mass ratio of the optimum condition as the amount of air is increased. Being present in large quantities results in an increase in the amount of the second fraction stream exiting the system and a decrease in the amount of the first fraction stream re-introduced.
- the manufacturing method according to an embodiment of the present invention may be to add oxygen (O 2 ) and nitrogen (N 2 ) contained in the reaction feed stream in the form of pure gas independent of each other, the independent
- the pure gas form may mean that oxygen (O 2 ) and nitrogen (N 2 ) are not introduced from air, which is a mixed gas, but are introduced in the form of pure oxygen gas and pure nitrogen gas, respectively.
- the oxygen may be introduced in the form mixed with air as necessary. That is, oxygen may be mixed with air (mixed gas in which the oxygen mass ratio is increased), or oxygen may be added while air is basically added.
- the first fraction stream which is re-introduced by reacting oxygen and nitrogen in the form of independent pure gas without introducing oxygen and nitrogen in the form of a mixed gas such as air, is generated after the reaction.
- the amount of each component included in the reaction raw material stream introduced into the reactor by measuring in real time the amount of butadiene and the active ingredient contained in the second fraction stream discharged to the outside of the system, in particular of one or more components selected from oxygen and nitrogen The amount can be adjusted individually. Therefore, the total amount of the second fraction stream discharged can be reduced, and as a result, it can be adjusted to minimize the amount of active ingredients such as butadiene contained in the second fraction stream and discharged to the outside of the system.
- the C4 fraction may mean the remaining C4 raffinate-1, 2, and 3 remaining after separating useful compounds from the C4 mixture produced by naphtha cracking, and means a C4 class that can be obtained through ethylene dimerization. It may be.
- the C4 fraction is n-butane, trans-2-butene, cis-2-butene and 1-butene It may be one or a mixture of two or more selected from the group consisting of (1-butene).
- the steam or nitrogen (N 2 ) in the oxidative dehydrogenation reaction may reduce the explosion risk of the reactants, and may be a diluent gas introduced for the purpose of preventing coking of the catalyst and removing the heat of reaction.
- the oxygen (O 2 ) may cause a dehydrogenation reaction by reacting with C4 fraction as an oxidant (oxidant).
- the method of introducing the reactant stream into the reactor is mixed with C4 fraction, steam, oxygen (O 2 ) and nitrogen (N 2 ) before entering the reactor in the form of a mixed reactant
- the C4 fraction, steam, oxygen (O 2 ), and nitrogen (N 2 ) may be introduced into the reactor through separate pipelines and uniformly mixed in the reactor.
- the reactant stream is the C4 fraction, steam, oxygen (O 2 ) and nitrogen (N 2 ) are mixed by a mixing device located in front of the reactor and then introduced into the reactor, or the C4 fraction, Steam, oxygen (O 2 ) and nitrogen (N 2 ) may be mixed in one pipeline connected to the reactor passing through a plurality of individual pipelines each branched to enter the reactor (see FIG. 2). .
- the C4 fraction, steam, oxygen and nitrogen contained in the reaction raw material stream may be introduced into the pipeline in a gaseous state, the gas is pre-heated to a temperature favorable for the oxidative dehydrogenation reaction May be
- the catalyst charged in the reactor is not particularly limited as long as it is capable of producing butadiene by oxidative dehydrogenation of the C4 fraction, for example ferrite catalyst or bismuth molybdate catalyst Can be.
- the catalyst may be a bismuth molybdate-based catalyst
- the bismuth molybdate-based catalyst is one selected from the group consisting of bismuth (Bismuth), molybdenum (Molybdenum) and cobalt (Cobalt)
- the bismuth molybdate catalyst may be a multicomponent bismuth molybdate catalyst.
- the type and amount of the reaction catalyst may vary depending on the specific conditions of the reaction.
- the reactor is not particularly limited as long as the oxidative dehydrogenation reaction can proceed.
- it may be a tubular reactor, a tank reactor, or a fluidized bed reactor.
- the reactor may be a fixed bed reactor or may be a fixed bed multi-tubular reactor or a plate reactor.
- the step b is for separating the main product from the mixed reaction product including the main product including butadiene obtained from the reactor and the incidental by-products, the step of separating the gas product and the C4 mixture containing butadiene.
- the separation may be performed through one or more steps selected from the group consisting of a compression step using a compressor, a dehydration step using a dehydration device, and a gas separation step using a gas separation device.
- the manufacturing method according to an embodiment of the present invention may perform the step of quenching the mixed reaction product obtained from the reactor using a quenching tower (quenching tower) before the separation step of step b.
- the mixed reaction product obtained from the reactor is
- It may be in the form of hot gases, and therefore needs to be cooled before being introduced into the gas separation device.
- the cooling method used in the quenching step is not particularly limited, but may be, for example, a cooling method of directly contacting the cooling solvent and the mixed reaction product, or a cooling method of indirectly contacting the cooling solvent and the mixed reaction product. It may be.
- the separation step according to an embodiment of the present invention is to contact the mixed reaction product obtained from the reactor with the absorption solvent in the absorption tower to selectively absorb only the C4 mixture containing butadiene in the absorption solvent, and other gas products (light gas) can be separated and removed.
- the C4 mixture including butadiene is selectively absorbed by the absorption solvent, and the remaining gas product is It goes through the pipe through the tower top.
- the kind of the absorption tower is not particularly limited, and may be, for example, a packed tower, a wet wall tower, a spray tower, a cyclone scrubber, a bubble tower, a bubble stirring tank, a single tower (bubble tower, porous plate tower) or a foam separation tower.
- an absorption solvent conventionally used in the art may be used.
- a saturated hydrocarbon of C 6 to C 10 an aromatic hydrocarbon of C 6 to C 8, or an amide compound may be used.
- the absorption solvent may be, for example, dimethylformamide (DMF), toluene, xylene, N-methyl-2-pyrrolidone (NMP), or the like.
- the gas product discharged through the pipe through the top of the absorption tower may be divided into a first fraction stream and a second fraction stream.
- the first fraction stream may be a concentrated stream comprising one or more selected from the group consisting of nitrogen and carbon dioxide, as described above, and may be circulated along an internal circulation line (see FIG. 2, FIG. 2) to be reintroduced into the reactor. (Step d).
- the first fractional stream may further include oxygen, steam, unreacted raw materials, butadiene, etc. in addition to the aforementioned components, and the carbon dioxide contained in the first fractional stream is re-introduced into the reactor through internal circulation to oxidize dehydration in the reactor. It can act as a mild oxidant or as a diluent gas in the digestion reaction.
- the second fraction stream is a purge stream discharged to the outside of the system, and is discharged to the outside of the system through a discharge line 4 (see FIG. 2) separate from the first fraction stream (step d).
- the second fraction stream may comprise nitrogen (N 2 ), carbon dioxide (CO 2 ), unreacted raw materials and butadiene, and the like.
- the mass of butadiene contained in the second fraction stream and discharged to the outside of the system may be in an amount corresponding to about 0.01% to 10% of the total amount of butadiene generated by the oxidative dehydrogenation reaction in the reactor.
- the absorbing solvent is used to selectively absorb only the C4 mixture including butadiene, but may also dissolve a portion of a gas such as nitrogen and carbon dioxide.
- a degassing step for removing gas such as nitrogen and carbon dioxide may be additionally performed, and the degassing step may be performed in a degassing tower.
- the degassing method is not particularly limited and may be by conventional methods used in the art.
- Step c is a step of purifying the C4 mixture containing butadiene to obtain a high purity butadiene.
- the purification step is a solvent separation and recovery device including a solvent recovery tower for separating and recovering the absorption solvent, a high boiling point removal tower for removing the high boiling point component, a solvent purification tower and the like, butadiene purification for the purification of high purity butadiene This may be accomplished through one or more devices selected from the towers.
- the method for separating and recovering the solvent is not particularly limited, and for example, a distillation separation method may be used.
- a distillation separation method an absorption solvent in which a C4 mixture including butadiene is dissolved is introduced into a solvent recovery tower by a reboiler and a condenser, followed by distillation.
- the distillation separation process extracts a C4 mixture containing butadiene from the vicinity of the column top.
- the absorbing solvent separated in the above process is extracted from the bottom of the solvent recovery column, and the extracted absorbing solvent may be re-injected into the shearing process and used again. Since the absorbing solvent may contain impurities, a part of the absorbing solvent may be extracted before recycling to remove impurities by a known purification method such as distillation, decantation, sedimentation, contact treatment with an adsorbent or an ion exchange resin, and the like. You may.
- the C4 mixture including butadiene separated from the absorption solvent may be introduced into the high boiling point removal tower for the separation of the high boiling point component.
- a process of removing a high boiling point component (a component having higher solubility than butadiene) is performed, and a component having a higher solubility than the butadiene is dissolved in a solvent.
- the solvent may be discharged from the bottom and transferred to the solvent purification tower.
- butadiene from which the high boiling point component is removed may be discharged from the top of the high boiling point removing tower and transferred to the butadiene purification tower.
- butadiene delivered to the purification tower may be obtained as high-purity butadiene by removing the high boiling point, low boiling point components during the purification tower.
- the purity of butadiene finally obtained through the series of steps may be 99.0% ⁇ 99.9%.
- An oxidative dehydrogenation reaction was performed by introducing a reactant stream into a reactor filled with a bismuth molybdate catalyst.
- the reactor used a metal tubular reactor.
- 1-butene, steam, oxygen and nitrogen were used as the reaction raw materials, the input ratio of the initial reaction raw materials was adjusted to the reaction conditions, and the mass ratio of oxygen and nitrogen thereafter was added as shown in Table 1 below.
- the reactor was designed so that steam was mixed with other reaction raw materials and introduced into the reactor.
- the amount of 1-butene was controlled using a mass flow controller for liquid, oxygen and nitrogen were controlled using a mass flow controller for gas, and the amount of steam was controlled using a liquid pump.
- the mixed reaction product was separated into a gas product and a C4 mixture containing butadiene through a separator.
- the butadiene-containing C4 mixture was further purified through a purification apparatus to prepare butadiene with a purity of 99.7% (yield 99.4%).
- the separated gas product was discharged to the outside of the system as a purge stream (second fraction stream), and the amount of butadiene in the active ingredient contained in the purge stream and discharged to the outside of the system is oxidative dehydrogenation reaction in the reactor. Corresponding to about 0.06% of the amount of butadiene produced by.
- Butadiene having a purity of 99.7% was prepared in the same manner as in Example 1, except that the mass ratio of oxygen and nitrogen introduced after the first was adjusted as shown in Table 1 below (yield 99.3%).
- the amount of butadiene in the active ingredient discharged to the outside of the system corresponded to about 0.2% of the amount of butadiene produced by the oxidative dehydrogenation reaction in the reactor.
- Butadiene having a purity of 99.7% was prepared in the same manner as in Example 1, except that oxygen and nitrogen were introduced as air as a mixed gas (yield 99.0%). At this time, the mass ratio of oxygen to nitrogen in the air was 0.3: 1.
- the amount of butadiene in the active ingredient discharged to the outside of the system corresponds to about 0.5% of the amount of butadiene produced by the oxidative dehydrogenation reaction in the reactor.
- Example 1 and Example 2 according to an embodiment of the present invention can be added to the oxygen and nitrogen independently in the reactor, the mass ratio of oxygen and nitrogen is added to the flexible It was confirmed that the mass ratio of nitrogen in the reactor can be easily adjusted in comparison with Comparative Example 1 in which oxygen and nitrogen are introduced into the air. In addition, it was confirmed that the total flow rate (Table 2) of the second fraction stream discharged to the outside of the system can be controlled by flexibly adjusting the mass ratio of the introduced oxygen and nitrogen, and as a result, the second fraction discharged to the outside of the system. By controlling the total amount of the stream it was confirmed that the amount of butadiene contained in it can be controlled out.
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Abstract
Description
구분 | 실시예 1 | 실시예 2 | 비교예 1 | |
산소(O2) 대 질소(N2) 외부 투입 질량비 | 3.28 | 0.78 | 0.30 | |
반응기 내 질량비 | 스팀(steam) 대 C4 유분 | 0.98 | 0.98 | 0.98 |
산소(O2) 대 C4 유분 비 | 0.49 | 0.49 | 0.49 | |
질소(N2) 대 C4 유분 비 | 3.93 | 5.07 | 5.36 | |
배출되는 부타디엔 내 순생성(반응) 부타디엔 비 | 0.0006 | 0.002 | 0.005 | |
부타디엔 최종 회수율(%) | 99.4 | 99.3 | 99.0 |
제2 분획 스트림(4) | ||||
구분 | 실시예 1 | 실시예 2 | 비교예 1 | |
총 유량(ton/hr) | 5.79 | 17.13 | 41.52 | |
질량비(wt%) | C4 성분 | 1.82 | 0.8 | 0.5 |
산소 | 1.62 | 1.8 | 1.9 | |
질소 | 57.96 | 84.2 | 92 | |
이산화탄소 | 37.31 | 12.4 | 4.9 | |
부타디엔 | 0.26 | 0.3 | 0.3 | |
기타 | 1.03 | 0.52 | 0.3 |
Claims (9)
- a) C4 유분, 스팀(steam), 산소(O2) 및 질소(N2)를 포함하는 반응원료 스트림을 촉매가 충진된 반응기 내에 유입시켜 산화탈수소화 반응을 진행시키는 단계;b) 상기 반응기로부터 얻어진 부타디엔을 포함하는 C4 혼합물과 가스 생성물(light gas)을 분리하는 단계; 및c) 상기 부타디엔을 포함하는 C4 혼합물을 정제하는 단계를 포함하고,상기 b) 단계의 가스 생성물을 제1 분획 스트림과 제2 분획 스트림으로 분리하여 상기 제1 분획 스트림은 반응기 내에 재유입시키고, 제2 분획 스트림은 계 외부로 배출시키는 단계 d)를 더 포함하며,상기 제1 분획 스트림은 질소 및 이산화탄소 중 어느 하나 이상을 포함하는 것인 산화탈수소화 반응을 통한 부타디엔의 제조방법.
- 청구항 1에 있어서,상기 반응원료 스트림에 포함되는 산소(O2) 및 질소(N2)는 서로 독립적인 순수 가스 형태로 투입되는 것인 산화탈수소화 반응을 통한 부타디엔의 제조방법.
- 청구항 1 에 있어서,상기 반응원료 스트림에 포함되는 산소(O2)는 공기(air)와 혼합된 상태로 투입되는 것인 산화탈수소화 반응을 통한 부타디엔의 제조방법.
- 청구항 1에 있어서,상기 반응기 내 반응조건은 C4 유분 : 스팀 : 산소 : 질소=1: 1 내지 9: 0.01 내지 3:3 내지 9의 질량비인 것인 산화탈수소화 반응을 통한 부타디엔의 제조방법.
- 청구항 1 에 있어서,상기 제1 분획 스트림의 총량은 반응원료 스트림 내 산소 및 질소의 질량비에 따라 조절되고,상기 반응원료 스트림 내 산소 및 질소의 질량비는 서로 독립적으로 조절되는 것인 산화탈수소화 반응을 통한 부타디엔의 제조방법.
- 청구항 1에 있어서,상기 이산화탄소(CO2)는 반응기 내에서 약산화제(mild oxidant) 또는 희석기체로 사용되는 것인 산화탈수소화 반응을 통한 부타디엔의 제조방법.
- 청구항 1 에 있어서,상기 제2 분획 스트림의 총량에 비례하여 손실되는 부타디엔의 총량이 조절되고,상기 제2 분획 스트림의 총량은 반응원료 스트림 내 산소 및 질소의 질량비에 따라 조절되며상기 반응원료 스트림 내 산소 및 질소의 질량비는 서로 독립적으로 조절되는 것인 산화탈수소화 반응을 통한 부타디엔의 제조방법.
- 청구항 7에 있어서,상기 손실되는 부타디엔의 총량은 반응기 내에서 산화탈수소화 반응으로 생성된 부타디엔 총량의 0.01% ~ 10%인 것인 산화탈수소화 반응을 통한 부타디엔의 제조방법.
- 청구항 1 에 있어서,상기 C4 유분은 n-부탄(n-butane), 트랜스-2-부텐(trans-2-butene), 시스-2-부텐(cis-2-butene) 및 1-부텐(1-butene)으로 이루어지는 군에서 선택되는 1종 이상인 것인 산화탈수소화 반응을 통한 부타디엔의 제조방법.
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