JP2013220998A - Method for producing lower olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a ≥3C olefin with a high yield by efficiently separating the ≥3C olefin which is an objective substance from a reaction mixture obtained by bringing a catalyst and a synthesis gas into contact with each other after suppressing increase in a cooling load in low temperature separation, in producing the ≥3C olefin by bringing the synthesis gas, whose principal ingredients are carbon monoxide and hydrogen, and the catalyst into contact with each other.SOLUTION: Carbon dioxide, methane, and a 2C component are separated from a reaction mixture obtained by bringing a catalyst and a synthesis gas into contact with each other through a membrane separation method or a low temperature separation method, and then unseparated components are separated and purified. By preliminarily separating COand ≤2C components composed of small molecules through the membrane separation method or the adsorption separation method, a cooling load in a subsequent low temperature separation can be reduced, and by suppressing azeotrope of propylene which is an objective substance and CO, loss of propylene can be reduced.

Description

  The present invention relates to a method for producing a lower olefin, which comprises producing an olefin having 3 or more carbon atoms by bringing a synthesis gas mainly composed of carbon monoxide and hydrogen into contact with a catalyst.

  In this specification, “C2 component”, “C3 component”, and “C4 component” indicate “component having 2 carbon atoms”, “component having 3 carbon atoms”, and “component having 4 carbon atoms”, respectively. The same applies to the case of C5 or higher. “C5 + component” and “C9 + component” indicate “component having C5 or more carbon atoms” and “component having 9 or more carbon atoms”, and “+” corresponds to “or more”.

Conventionally, the production of lower olefins containing propylene and butene has been mainly produced by naphtha crackers, but in the future, it is recognized that petrochemical technology using natural gas or coal as raw materials will be important. In recent years, research has been actively conducted. Fischer-Tropsch (Fischer-Tropsch) reaction, which is a process for producing synthesis gas from methane and coal and producing lower olefin directly from the resulting synthesis gas (Hereinafter referred to as “FT reaction”) and a process for producing olefin from synthesis gas via methanol (Methanol-To-Olefin; hereinafter referred to as “MTO”) are known. However, MTO that produces olefins via methanol is not economical because it requires three steps: (1) synthesis gas production, (2) methanol production, and (3) olefin production.
Therefore, a process for producing a lower olefin directly from synthesis gas without passing through methanol is preferred.

As a technique for directly producing a lower olefin from synthesis gas, for example, an iron catalyst described in Patent Documents 1 and 2 is used, and an FT reaction and a water gas shift reaction are performed according to the following reaction formulas (i) and (ii). A method of selectively producing a lower olefin by a combined reaction is mentioned.
n · CO + 2n · H ₂ → (CH ₂ =) _n (*) + n · H ₂ O (i)
CO + H ₂ O → CO ₂ + H ₂ (ii)
(* Represents an olefin having n carbon atoms)

For example, Patent Document 1 describes that after the FT reaction, CO ₂ is removed, and then subjected to a separation process to obtain a target olefin. Patent Document 2 describes a method of obtaining a target olefin after separating and removing CO ₂ together with hydrogen, methane and the like after the FT reaction.

US2011 / 0118365 International Publication WO2009 / 051353 Pamphlet

The above prior art has the following problems.
(1) Use of a catalyst with high propylene and butene selectivity (hereinafter sometimes referred to as “C3 / C4 olefin selectivity”) to improve the production of propylene and butene, which are the target products, will result in product distribution. Shifts to the lower hydrocarbon side, increasing the amount of C2 components such as methane, ethane, and ethylene. When these lower hydrocarbons increase, the cooling load increases in ordinary cryogenic (distillation) separation when separating propylene and butene as products.
(2) As a characteristic of the above reaction, a large amount of CO ₂ is produced in the product according to the above reaction formula (ii). However, since CO ₂ azeotropes with propylene, which is the main target, A distillation column is required. Furthermore, there is a problem that the separation energy is large and the loss of propylene is also large.

  In the present invention, when a synthesis gas mainly composed of carbon monoxide and hydrogen is brought into contact with a catalyst to produce a C3 or higher olefin, a cryogenic separation is performed from a reaction mixture obtained by bringing the catalyst and the synthesis gas into contact with each other. An object of the present invention is to provide a method for producing a lower olefin by efficiently separating an olefin of C3 or higher, which is a target product, in a high yield after suppressing an increase in cooling load in .

As a result of intensive studies to solve the above-mentioned conventional problems, the present inventors do not carry out all separation of products by cryogenic separation, but rather cryogenic separation of propylene and butene, which are target products. prior to performing, small C2 following ingredients of CO ₂ and molecular, by previously separated in advance by membrane separation or adsorption separation method, it is possible to reduce the cooling load in the subsequent cryogenic separation, also the desired product Depending on the situation, the distillation column for demethanization can be omitted, the scale of the distillation column for deethanation can be reduced, and the azeotrope of propylene and CO _{2 as} the target product can be suppressed. Loss can be reduced, and furthermore, when a Fe—Cu—Mo / graphite catalyst is used as a catalyst, high propylene and butene selectivity can be obtained, so that production efficiency is further improved. And, it was found.

  The present invention has been achieved on the basis of such findings, and the gist thereof is as follows.

[1] In a method for producing a lower olefin in which a synthesis gas mainly comprising carbon monoxide and hydrogen is brought into contact with a catalyst to produce an olefin having 3 or more carbon atoms, the reaction mixture is brought into contact with the catalyst and the synthesis gas. A first step of obtaining, a second step of separating carbon dioxide, methane, and a carbon number 2 component from the reaction mixture by a membrane separation method or an adsorption separation method, and the second step was not separated. And a third step of separating and refining the components.

[2] The method for producing a lower olefin according to [1], including a step of separating water from the reaction mixture before the second step.

[3] The method for producing a lower olefin according to [1] or [2], comprising a step of separating a component having 9 or more carbon atoms from the reaction mixture before the second step.

[4] The catalyst according to any one of [1] to [3], wherein the catalyst contains iron, copper, and molybdenum as active components, and the active components are supported on graphite. A method for producing a lower olefin.

[5] The hydrogen / carbon monoxide molar ratio of the synthesis gas in the first step is 0.1 or more and 4 or less, according to any one of [1] to [4] A method for producing a lower olefin.

[6] In any one of [1] to [5], in the first step, a reaction temperature when the catalyst and the synthesis gas are contacted is 200 ° C. or more and 400 ° C. or less. The manufacturing method of lower olefin as described.

[7] In the first step, the reaction pressure when the catalyst and the synthesis gas are brought into contact with each other is 0.1 MPa or more and 5 MPa or less in absolute pressure. The manufacturing method of the lower olefin in any one.

  According to the present invention, when a synthesis gas mainly composed of carbon monoxide and hydrogen is brought into contact with a catalyst to produce a C3 or higher olefin, a reaction mixture obtained by bringing the catalyst into contact with the synthesis gas is After suppressing the increase in the cooling load in the cold separation, the target C3 or higher olefin can be efficiently separated to obtain the C3 or higher olefin in a high yield.

It is the isolation | separation model figure used by the product isolation | separation energy simulation in Examples 9 and 10 and Comparative Examples 1-4.

  Hereinafter, embodiments of the method for producing a lower olefin of the present invention will be described in detail.

  The method for producing a lower olefin of the present invention comprises the step of producing a olefin having 3 or more carbon atoms by bringing a synthesis gas mainly composed of carbon monoxide and hydrogen into contact with the catalyst. A second step of separating carbon dioxide, methane, and a carbon number 2 component from the reaction mixture by a membrane separation method or an adsorption separation method, and the second step And a third step of separating and purifying the components that were not separated in the step, specifically, including the following steps (1) to (4), and further including the following steps: (5) to (9) may be included, and it is particularly preferable that steps (5) and (6) are included.

(1) A synthesis gas is produced by reforming from a raw material hydrocarbon gas and a gas containing CO ₂ .
(2) The synthesis gas produced in (1) is brought into contact with a catalyst, preferably an Fe-based catalyst, more preferably an Fe—Cu—Mo / graphite catalyst described later, and a reaction mixture containing a lower olefin and CO ₂ (reaction product) Gas).
(3) Using the separation membrane method or the adsorption separation method, the reaction mixture obtained in (2) is carbon dioxide, methane and C2 components (hereinafter, these may be referred to as “gas components”), specifically Specifically, it is separated into a gas component containing H ₂ , CO, CO ₂ , methane (CH ₄ ), ethylene (C ₂ H ₆ ), and ethane (C ₂ H ₈ ), and a component of C3 or higher.
(4) The C3 or higher component obtained in (3) is further separated and purified by cryogenic separation to obtain propylene, butene and the like.

(5) The reaction mixture produced in (2) is cooled and separated into a C9 or higher component, preferably a C7 or higher component, and other components by gas-liquid separation.
(6) Water is removed from the reaction mixture obtained in (2) and / or the component other than the C9 or higher component obtained in (5), preferably the C7 or higher component.
(7) C9 or higher component separated in (5), preferably C7 or higher component is used as fuel.
(8) At least a part of the gas components (CO ₂ , CH ₄ , C2 components) obtained in (3) is recycled as the reforming raw material in (2) through (1) and / or a reverse shift reaction described later. To do.
(9) In (7), at least a part of CO ₂ recovered from the combustion exhaust gas discharged by the combustion of fuel using a C9 or higher component, preferably a C7 or higher component, is used as the reforming raw material in (1).

<Step (1)>
In step (1), synthesis gas containing CO and H ₂ as main components is produced by reforming from a raw material gas containing hydrocarbon gas and CO ₂ . Here, as the raw material gas, a known raw material for synthesis gas can be used. For example, a lower hydrocarbon such as methane or ethane, natural gas, naphtha, coal, coke oven gas, or the like can be used. it can.
In addition to the hydrocarbon gas and CO ₂ , the raw material gas may contain water, H ₂ , and O ₂ , and the above components can be appropriately added and used as necessary.
In addition, the gas components (CO ₂ , CH ₄ , C 2 components) separated in the later-described step (3) may be recycled and mixed and used for this source gas (step (8)). may be used as a mixture of CO ₂ recovered from the combustion exhaust gas discharged by the fuel of step (7) (step (9)).

In this invention, it is made to contact with the below-mentioned catalyst and a reaction mixture is obtained. The molar ratio of H ₂ / CO in this synthesis gas is not particularly limited, but is usually 0.1 or more, preferably 0.5 or more, usually 4 or less, preferably 2 or less, more preferably 1 or less.
If the H ₂ / CO molar ratio of the synthesis gas is less than 0.1, the CO conversion rate in the reaction formula (i) may be low, and the contribution of the CO disproportionation reaction occurring in parallel may increase. When it exceeds 4, the hydrogenation reaction of the produced | generated olefin will advance easily and the selectivity of an olefin may fall.

During this synthesis _gas, other _{H 2, CO, CH 4,} CO 2, O 2, N 2, H 2 O , etc. may be included, in the synthesis gas _{H 2} and CO total of The content is preferably 40 mol% or more, particularly preferably 50 mol% or more. If the contents of H ₂ and CO in the synthesis gas are too small, the reactor size increases, which may lead to increased costs.

The molar ratio of H ₂ / CO in the synthesis gas is determined by separating and removing H ₂ from the synthesis gas generated by the reforming, or using a reverse shift reaction according to the following reaction formula (iii) at the time of reforming. Thus, it is possible to adjust to the above range.
CO ₂ + H ₂ → CO + H ₂ O (iii)
Moreover, not only the combined use at the time of the reforming described above, but it is also possible to adjust by separately providing a reverse shift reactor and introducing CO produced there.
The total content of H ₂ and CO in the synthesis gas is more than the above lower limit value by controlling the conversion rate in the reforming reaction, controlling the amount of recycle gas, gas-liquid separation with a flash drum, etc. It can be.

<Step (2)>
In step (2), the synthesis gas obtained in step (1) is brought into contact with a catalyst to obtain a reaction mixture (reaction product gas) (FT reaction).

(catalyst)
The catalyst used in the FT reaction is not particularly limited as long as it can contact the synthesis gas and produce olefin, but from the viewpoint of excellent selectivity of C3 olefin and C4 olefin, Fe is the main component. It is preferable to use a catalyst (described in Patent Documents 1 and 2). In particular, Fe as a main component as an active component, Cu and Mo as subcomponents, and these active components are supported on a graphite carrier. (Hereinafter referred to as “Fe—Cu—Mo / graphite catalyst”) is preferable.

  In the Fe—Cu—Mo / graphite catalyst, the Fe particle diameter measured by SEM observation is preferably 10 to 500 nm, particularly preferably 10 to 300 nm. If the particle size of Fe is too large, Fe which is an active ingredient to be used may not be used effectively. If it is too small, it tends to aggregate and decrease its activity. The amount of Fe supported on graphite is preferably graphite: Fe = 1: 0.05 or more, particularly 1: 0.1 or more and 1: 9 or less in terms of the weight ratio of graphite to Fe. If the amount of Fe supported on graphite is too small, sufficient catalytic activity may not be obtained. If the amount is too large, the productivity of the catalyst may deteriorate.

Further, the supported amount of Cu is preferably 0.1 to 10% by weight, particularly 0.5 to 2% by weight, based on Fe. If the supported amount of Cu is too small, sufficient catalytic activity may not be obtained, and if it is too much, the CO conversion tends to decrease.
The amount of Mo supported is preferably 0.1 to 20% by weight, particularly 1 to 10% by weight, based on Fe. If the amount of Mo supported is too small, sufficient C3 / C4 olefin selectivity may not be obtained, and if it is too large, the CO conversion rate may decrease.

Such an Fe—Cu—Mo / graphite catalyst is produced by a precipitation method as shown in Preparation Example 1 below, and as shown in Preparation Example 2 below. The obtained Fe—Cu / graphite catalyst can be produced by supporting Mo by an impregnation method.
The obtained Fe—Cu—Mo / graphite catalyst is subjected to a reduction treatment with H ₂ or H ₂ / CO mixed gas, and then subjected to the reaction.

(Reaction conditions)
The reaction conditions for bringing the synthesis gas into contact with the above catalyst are not particularly limited, but are preferably as follows.
Reaction temperature: 200-400 ° C, preferably 240-300 ° C
Reaction pressure: 0.1 to 10 MPa, preferably 0.5 to 5 MPa
When the reaction temperature is less than the above lower limit, the progress of the FT reaction and the water gas shift reaction may be slow, and when the reaction temperature exceeds the upper limit, the catalyst deterioration may be remarkable. Further, if the reaction pressure is less than the above lower limit, the progress of the FT reaction and the water gas shift reaction tends to be slow, and the methane selectivity tends to increase. If the reaction pressure exceeds the upper limit, the C3 / C4 olefin selectivity may be reduced, There is a tendency that the deterioration of becomes remarkable. In addition, a high-pressure reactor may be required, and the equipment cost may increase.

The form of the FT reaction is not particularly limited, but is usually carried out by a flow reaction. Specific examples include a fixed bed, a fluidized bed, and a slurry bed. A slurry bed is preferable because it is easy to control the reaction temperature and regenerate the catalyst.
The space velocity GHSV of the source gas is usually 500 to 200,000 (h ⁻¹ ), preferably 1000 to 100,000 (h ⁻¹ ).

The reaction results of such FT reaction are preferably as follows.
The selectivity here is the selectivity in terms of carbon atoms, and the selectivity of hydrocarbons other than CO ₂ is (total number of carbons contained in the target product) / (excluding CO ₂ from the obtained compound). (Total carbon number) × 100.
CO conversion: 20% or more, 90% or less CO ₂ selectivity: 20% or more, 50% or less Selectivity of hydrocarbons other than CO ₂
C1 component: 1 to 20%
C2 olefin: 2-20%
C2 paraffin: 1-10%
C3-C4 olefin: 20-90%
C3-C4 paraffin: 2-10%
C5-C8 component: 1-40%
C9 or higher component: 1-30%

<Step (3)>
In step (3), CO ₂ , CH ₄ and C2 components (gas components) are separated from the reaction mixture obtained in step (2) by a separation membrane method or an adsorption separation method. At this time, most of the gas components may be separated from the reaction mixture. Prior to this step (3), it is preferable to separate components of C9 or higher, preferably C7 or higher, by cooling and gas-liquid separation (step (5)). Thus, in advance, the components of C9 or higher, preferably By separating the C7 or higher component, it is possible to prevent the separation inhibition when the gas component is separated by the membrane separation method or the adsorption separation method and the deterioration of the used separation membrane or the adsorbent. Further, the component C9 or higher, preferably C7 or higher, separated here is preferably used as fuel for the reforming reactor, boiler or the like (step (7)) and discharged at this fuel supply destination. CO ₂ in the combustion exhaust gas is preferably recovered and used as a reforming raw material (step (9)).

  Further, prior to step (3), water in the reaction mixture is removed from the reaction mixture after step (2) by cooling and gas-liquid separation, and / or in step (5), C9 or more components Preferably, it is preferable to separate the water from the component after removing the component C7 or higher by an adsorption separation method, and both the reaction mixture in step (2) and the component in step (5) can be separated from water. More preferably (step (6)), separation of water in advance in this way also prevents separation when separating gas components by membrane separation or adsorption separation, and deterioration of the separation membrane or adsorbent used. Can be prevented.

  In the present invention, when the gas component is separated from the reaction mixture by a membrane separation method, the separation membrane to be used is not particularly limited as long as it has excellent separation performance between the C2 component and the C3 component. Y. Panetal. Chem. Commun. , 2011, 47, 10275; Huang, J. et al. Am. Chem. Soc. , 2010, 132, 2140. In particular, silica membranes, zeolite membranes, organic-inorganic hybrid membranes and the like can be used.

  Further, when the gas component is separated from the reaction mixture by the adsorption separation method, zeolite (molecular sieve), silica, alumina, activated carbon, or the like can be used as the adsorbent.

The gas component separated in the step (3) is recycled as a reforming raw material gas after the water is separated if necessary (step (8)). In the recycling of this gas component, the gas species to be recycled can be appropriately selected depending on the catalyst performance, CO ₂ price, CO ₂ utilization target value, membrane separation performance or adsorption separation performance, boosting power, and separation power.
Further, CO ₂ contained in the gas component can be reacted with H _{2 in a} reverse shift reactor to produce a mixed gas of H ₂ and CO, which can be recycled to the FT reactor (step (8)).

  C3 or higher component after separating the gas component in this step (3) is usually C2 or lower component 8% or lower, propylene 40 to 60%, butene 20 to 30%, C5 or higher component 2 to 30% by mole fraction. Is included.

<Process (4)>
The C3 or higher component obtained in step (3) is subjected to cryogenic (distillation) separation according to a conventional method, and propylene and butene are separated and recovered.

  According to the method for producing a lower olefin of the present invention, 70% or more of the propylene in the C3 or higher component separated by the membrane separation method or the adsorption separation method in the step (3) is used in the step (3). It can be recovered by the cryogenic separation of 4), and the distillation temperature at that time can be raised to reduce the cooling load.

  Hereinafter, the present invention will be described more specifically with reference to examples.

[Preparation of catalyst]
<Preparation Example 1: Preparation of Fe-Cu / graphite catalyst>
Fe-Cu / graphite catalyst was prepared by coprecipitation method.
To a 500 mL four-necked flask, 300 mL of ion-exchanged water and 5 g of graphite powder (HSAG-100, manufactured by TIMCAL) were added and heated to 70 ° C. in an oil bath while stirring. Nitrogen flow was started simultaneously with the start of heating, and the inside of the system was replaced with nitrogen gas. When a predetermined temperature is reached, a mixed solution of 1 mol / L FeSO ₄ (iron sulfate special grade, manufactured by Kishida Chemical Co.) aqueous solution and 0.5 mol / L CuSO ₄ (copper sulfate special grade, manufactured by Kishida Chemical Co.) aqueous solution, pH the aqueous solution of _Na 2 CO ₃ 2 mol / L for adjustment, was added dropwise to a pH of 8.0 to 8.2. At this time, the ratio of graphite to Fe was adjusted to graphite: Fe = 1: 1 by weight, and the liquid amount was adjusted so that Cu was 1 wt% with respect to Fe.
After completion of dropping, the mixture was stirred at 70 ° C. for 3 hours while continuing the nitrogen flow. After allowing to cool, the liquid and the precipitate were separated by pressure filtration under a nitrogen gas atmosphere, and the precipitate was sufficiently washed with ion-exchanged water. After washing, it was put in a vacuum dryer and vacuum dried at room temperature for 1 hour. After vacuum drying, it was dried at 110 ° C. for 12 hours under a nitrogen stream, and then calcined at 400 ° C. for 3 hours under a nitrogen stream.
The Fe particle diameter of the obtained Fe—Cu / graphite catalyst was about 10 to 300 nm.

<Preparation Example 2: Preparation of Fe-Cu-Mo (1) / graphite catalyst>
Mo was supported on the Fe—Cu / Graphite catalyst obtained in Preparation Example 1 by the impregnation method.
Put an Fe-Cu / Graphite catalyst and ammonium paramolybdate (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) in an amount of 1% by weight of Mo with respect to the amount of Fe in the eggplant flask, and add an appropriate amount of demineralized water. Sonication was performed for minutes. Thereafter, it was evaporated to dryness using a rotary evaporator, dried under a nitrogen stream at 110 ° C. for 12 hours, and then calcined at 400 ° C. for 3 hours to obtain an Fe—Cu—Mo (1) / graphite catalyst.

<Preparation Example 3: Preparation of Fe-Cu-Mo (2) / graphite catalyst>
Fe—Cu—Mo (2) / graphite was prepared in the same manner as in the preparation of Fe—Cu—Mo (1) / graphite in Preparation Example 2, except that the amount of supported Mo was 2% by weight with respect to Fe. A catalyst was obtained.

<Preparation Example 4: Preparation of Fe-Cu-Mo (5) / graphite catalyst>
Fe—Cu—Mo (5) / graphite was prepared in the same manner as in the preparation of Fe—Cu—Mo (1) / graphite in Preparation Example 2, except that the amount of supported Mo was 5% by weight with respect to Fe. A catalyst was obtained.

<Preparation Example 5: Preparation of Fe-Cu-Mo (10) / graphite catalyst>
The Fe—Cu—Mo (10) / graphite catalyst was prepared in the same manner as Fe—Cu—Mo (1) / graphite in Preparation Example 2 except that the amount of Mo supported was 10% by weight with respect to Fe. Obtained.

[Evaluation of catalytic activity]
<Example 1>
(Catalyst pretreatment)
Fe-Cu-Mo (1) /0.8 g of graphite catalyst was put into a firing tube having a bulb, heated from room temperature to 330 ° C. in an H ₂ (50 mL / min) stream over 60 minutes, and 6 at 330 ° C. Held for hours. After the release, it was replaced with Ar, and the firing tube valve was closed and stored so that air was not mixed.

(Batch reaction)
A stirrer and solvent (hexadecane 10 mL) were placed in a stainless steel micro autoclave (MAC) with an internal volume of 70 mL, and after Ar substitution, the pretreated Fe—Cu—Mo (1) / graphite catalyst was not exposed to air. Added with care. At this time, the calcined tube was weighed before and after the catalyst was charged, and the difference was defined as the weight of the catalyst used. The catalyst weight was 0.6 to 0.7 g.
The MAC was sealed, and the system was replaced with a reaction gas H ₂ / CO mixed gas (H ₂ 19 vol%, CO 78 vol%, Ar 3 vol%), and then the same gas was introduced up to 2 MPa. This MAC was inserted into a furnace that had been heated to 260 ° C. in advance, and after 15 minutes had elapsed, the reaction was started and allowed to react for 3 hours. After completion of the reaction, the mixture was air-cooled to room temperature, and the gas component and liquid component in the MAC were analyzed.

<Conversion rate, selectivity>
Conversion and selectivity were determined by gas chromatographic analysis based on the following conditions. The selectivity is the selectivity in terms of carbon atoms, and the selectivity for hydrocarbons other than CO ₂ is
(Total number of carbons contained in target product) / (Total number of carbons excluding CO ₂ from the obtained compound) × 100
It is represented by
The analysis conditions for each component are as follows.
<Analysis of Ar, CO, CO ₂ and CH ₄ >
Analyzer: Shimadzu gas chromatograph analyzer GC8A
Detector: TCD
Column: Active Carbon 60/80
Carrier gas: He
<Analysis of hydrocarbon gas components>
Analyzer: GL Science Gas Chromatograph Analyzer GC-4000
Detector: FID
Column: CP-PoraPLOTQ-HT
Carrier gas: He
<Analysis of hydrocarbon liquid components>
Analyzer: Shimadzu gas chromatograph analyzer GC-2014
Detector: FID
Column: CBP-1
Carrier gas: He

<Example 2>
The catalytic activity was evaluated in the same manner as in Example 1 except that the catalyst used was Fe-Cu-Mo (2) / graphite catalyst.

<Example 3>
The catalytic activity was evaluated in the same manner as in Example 1 except that the catalyst used was Fe-Cu-Mo (5) / graphite catalyst.

<Example 4>
The catalyst activity was evaluated in the same manner as in Example 1 except that the catalyst used was an Fe—Cu—Mo (5) / graphite catalyst and the reaction time was 6 hours.

<Example 5>
The catalyst activity was evaluated in the same manner as in Example 1 except that the catalyst used was an Fe—Cu—Mo (10) / graphite catalyst and the reaction time was 6 hours.

<Example 6>
The catalytic activity was evaluated in the same manner as in Example 1 except that the catalyst used was an Fe—Cu / graphite catalyst.

The results obtained by the batch reaction are shown in Table 1-A.
As apparent from Table 1-A, compared to Example 6 using Fe-Cu / graphite catalyst, Fe-Cu-Mo / graphite catalyst with 1 to 10% by weight of Mo added to Fe was used. In Examples 1 to 5, high-boiling components were reduced, and the selectivity of C3 and C4 olefins was increased. From this result, it is clear that the Fe—Cu—Mo / graphite catalyst is more advantageous for producing C3 and C4 olefins than the Fe—Cu / graphite catalyst.

<Example 7>
(Distribution reaction)
A solvent (100 mL of hexadecane) and 1 g of Fe—Cu—Mo (1) / graphite catalyst were placed in a 200 mL stainless steel autoclave equipped with a stirring blade, and a reaction gas (H ₂ 48.5% by volume, CO 48) was added to the system. And 5 vol%, Ar 3 vol%). Thereafter, the reaction gas was flowed at a rate of 150 mL / min, the pressure was increased to 0.5 MPa by a back pressure valve, and then the temperature was increased to 330 ° C. After the temperature and pressure became constant, reduction was performed for 4 hours. After the reduction, the reaction was started at a reactor temperature of 260 ° C. and a reaction pressure of 2.0 MPa. After confirming the end of the induction period, the activity was evaluated when the conversion rate was stable. “Time” described in Table 1-B indicates the time from the start of the reaction to the time when the activity was evaluated.

The analysis conditions for each component are as follows.
<Analysis of Ar, CO, CO ₂ and CH ₄ >
Analyzer: Shimadzu gas chromatograph analyzer GC-14A
Detector: TCD
Column: Active Carbon 60/80
Carrier gas: He
<Analysis of hydrocarbon gas components>
Analyzer: Shimadzu gas chromatograph analyzer GC-14B
Detector: TCD
Column: PorapakQ
Carrier gas: He
<Analysis of hydrocarbon liquid components>
Analyzer: Shimadzu gas chromatograph analyzer GC-2014
Detector: FID
Column: CBP-1
Carrier gas: He
The conversion rate and selectivity of each component were calculated based on the gas chromatograph.

<Example 8>
The catalytic activity was evaluated in the same manner as in Example 7 except that the catalyst used was an Fe—Cu / graphite catalyst.

The results obtained by the flow reaction are shown in Table 1-B.
As is apparent from Table 1-B, the Fe-Cu-Mo / graphite catalyst was used in which 1 wt% of Mo was added to Fe as compared with Example 8 using the Fe-Cu / graphite catalyst. In Example 7, the high boiling point component decreased and the selectivity of C3, C4 olefin increased. From this, it is apparent that the Fe—Cu—Mo / graphite catalyst is more advantageous for producing C3 and C4 olefins than the Fe—Cu / graphite catalyst in the flow reaction.

[Product separation energy simulation]
<Separation model and assumption>
From the results of Example 1 using an Fe—Cu—Mo / graphite catalyst and Example 6 using an Fe—Cu / graphite catalyst, the energy required for product separation per 1 kmol / hr of CO feedstock was estimated. . In the simulation, a separation model as shown in FIG. 1 was assumed. The fluid flow in the separation membrane module during the separation simulation was assumed to be cocurrent. ASPEN Tech ASPENPlus V7.2 was used for the calculation.
In the present specification, the selectivity, recovery rate, and concentration of the product in the simulation are expressed in terms of mole unless otherwise specified.

In addition, the specification of each apparatus was assumed as follows.
<Distillation tower C-1>
Theoretical plate number: 30
Tower bottom C2 concentration: 0.01 mol% vs C3
<Distillation tower C-2>
Theoretical plate number: 30
Tower top C4 concentration: 0.1 mol% vs C3
Tower bottom C3 concentration: 0.1 mol% vs C4
<Distillation tower C-3>
Theoretical plate number: 30
Tower top C5, 6 concentration: 0.1 mol% vs C4
<Separation membrane module (cocurrent flow model)>
CO ₂ separation: CO ₂ / (C ₂ + CH ₄ + CO) α = 100
CO ₂ / C ₃ α = 1000
CO ₂ + C ₂ separation: CO ₂ / (C ₂ + CH ₄ + CO) α = 10
C ₂ / C ₃ α = 100
Α represents a permeability coefficient ratio, which is an index of separation membrane performance.
Supply side pressure: 1.6 MPa
Permeation side pressure: 0.1 MPa

<Comparative Example 1>
Based on the reaction results obtained in Example 1, the calculation result was obtained in the case where the separation was performed only by the cryogenic separation without removing CO ₂ .

<Comparative example 2>
Based on the reaction results obtained in Example 1, after removing CO ₂ , the calculation results when separated by deep cold separation were determined.

<Comparative Example 3>
Based on the reaction results obtained in Example 6, the calculation results were obtained in the case of separation only by deep cooling separation without removing CO ₂ .

<Comparative example 4>
Based on the reaction results obtained in Example 6, the calculation result was obtained when CO ₂ was removed and then separated by deep cooling.

<Example 9>
Based on the reaction results obtained in Example 1, the calculation results when the components up to C2 were separated were obtained.

<Example 10>
Based on the reaction results obtained in Example 6, the calculation results when the components up to C2 were separated were obtained.

<Comparison of calculation results>
Based on the above assumptions, the recovery rate and required energy were calculated for a system (invention method) that separates the C2 component and lower in advance before the cryogenic separation and a system that separates only CO ₂ (prior art). The calculation results are summarized in Tables 2 to 4. The contents of each item are as follows.

Residual concentration: Stream-2 remaining without being separated by the membrane separation module M in the previous stage
Concentration of target gas in the tank C3 = recovery rate: of propylene introduced into the separation membrane module M, top of the distillation column C-2
Of propylene recovered in stream-4 of
C-1top temperature: top temperature (° C) of distillation column C-1
Cooling load: total amount of heat of condensation of distillation column C-1 per unit time (kcal / hr)

As is clear from Table 2, Comparative Examples 2 and 4 in which only CO ₂ was separated by the conventional method (Patent Document 1) were compared with Comparative Examples 1 and 3 in which CO ₂ was not separated, respectively. In all cases, the cooling load is reduced.
In addition, when a Fe—Cu—Mo / graphite catalyst having high selectivity for the C3 and C4 components is used from Table 2, the cooling load increases when CO ₂ is separated compared to the Fe—Cu / graphite catalyst. I understand that
Specifically, it increases about 60 to 80 kcal / hr when the cooling load is the reflux ratio 0.1, and increases about 300 to 470 kcal / hr when the cooling ratio is 1.0. Moreover, since the top temperature of the distillation column C-1 needs to be controlled in the range of −30 to −60 ° C. regardless of whether or not CO ₂ is separated, a refrigerator is necessary.
That is, it can be seen that the cooling load increases as the yield of the C3 and C4 components is improved in the conventional method.

  As is clear from Table 3, even in the system in which the selectivity of the C3 and C4 components is high and the product distribution has many lower components, the cooling load is very high in Example 9 in which the components up to C2 are separated in advance. It is small and is about 1/10 to 1/15 compared with the comparative example 2 which is a conventional method. Moreover, in the operation at a reflux ratio of 0.1 in Example 9, although the recovery rate of propylene is slightly lowered, the top temperature of the C-1 distillation column is between -0.2 to + 8.8 ° C. In addition, since the scale of the refrigerator can be reduced, the equipment cost can be reduced.

As is apparent from Table 4, in the method of the present invention, when the Fe-Cu-Mo / graphite catalyst having a high selectivity for the C3 and C4 components and a large amount of the lower components is used, Fe having a lower lower component selectivity is used. -Although the cooling load increases as compared with the case of using a Cu / graphite catalyst, the increase amount is about 2 to 8 kcal / hr when the reflux ratio is 0.1, and 10% even when the reflux ratio is 1.0. It remained at about 30 kcal / hr. As described above, in the Fe—Cu—Mo / graphite catalyst used in Example 9, when the reflux ratio is 0.1, the top temperature of the C-1 distillation column is −0.2 to + 8.8 ° C. Since the scale of the refrigerator can be reduced, the equipment cost is reduced.
From the above results, by carrying out the present invention using a catalyst having a high selectivity for C3 and C4 olefins by removing C2 and lower components before cryogenic separation, and obtaining C3 and C4 olefins in high yield, It is clear that the cooling load can be reduced.

C-1, C-2, C-3 Distillation tower M Separation membrane module

Claims (7)

  In a method for producing a lower olefin, wherein a synthesis gas mainly comprising carbon monoxide and hydrogen is brought into contact with a catalyst to produce an olefin having 3 or more carbon atoms, a first reaction mixture is obtained by bringing the catalyst into contact with the synthesis gas. Separating the carbon dioxide, methane, and carbon 2 components from the reaction mixture by membrane separation or adsorption separation, and components not separated in the second step And a third step of purification, comprising the step of producing a lower olefin.   The method for producing a lower olefin according to claim 1, comprising a step of separating water from the reaction mixture before the second step.   The method for producing a lower olefin according to claim 1 or 2, comprising a step of separating a component having 9 or more carbon atoms from the reaction mixture before the second step.   4. The lower olefin according to claim 1, wherein the catalyst contains iron, copper, and molybdenum as active components, and the active components are supported on graphite. 5. Production method.   5. The lower olefin of any one of claims 1 to 4, wherein a molar ratio of hydrogen / carbon monoxide of the synthesis gas in the first step is 0.1 or more and 4 or less. Production method.   The lower temperature according to any one of claims 1 to 5, wherein in the first step, a reaction temperature when the catalyst and the synthesis gas are brought into contact with each other is 200 ° C or higher and 400 ° C or lower. Production method of olefin.   7. The method according to claim 1, wherein in the first step, a reaction pressure when the catalyst and the synthesis gas are brought into contact is 0.1 MPa or more and 5 MPa or less in absolute pressure. The manufacturing method of lower olefin as described.

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