JPH0468292B2 - - Google Patents
Info
- Publication number
- JPH0468292B2 JPH0468292B2 JP61102471A JP10247186A JPH0468292B2 JP H0468292 B2 JPH0468292 B2 JP H0468292B2 JP 61102471 A JP61102471 A JP 61102471A JP 10247186 A JP10247186 A JP 10247186A JP H0468292 B2 JPH0468292 B2 JP H0468292B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- catalyst
- synthesis gas
- stream
- hour
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 230000015572 biosynthetic process Effects 0.000 claims description 42
- 238000003786 synthesis reaction Methods 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 239000003054 catalyst Substances 0.000 claims description 39
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 15
- 239000005977 Ethylene Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims 1
- 239000010948 rhodium Substances 0.000 claims 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 75
- 239000007789 gas Substances 0.000 description 29
- 229910052799 carbon Inorganic materials 0.000 description 21
- 235000019441 ethanol Nutrition 0.000 description 21
- 238000006297 dehydration reaction Methods 0.000 description 14
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 14
- 230000018044 dehydration Effects 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 229910004298 SiO 2 Inorganic materials 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910011212 Ti—Fe Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000010420 art technique Methods 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Description
【発明の詳細な説明】
〔技術分野〕
本発明は、エタノール合成用触媒とアルコール
脱水用触媒を組み合わせた複合触媒により、合成
ガスから一段でエチレンを選択的に合成する方法
に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a method for selectively synthesizing ethylene from synthesis gas in one step using a composite catalyst that combines a catalyst for ethanol synthesis and a catalyst for alcohol dehydration.
近年石油資源の枯渇化に伴い、石油以外の炭素
資源から石油化学製品を作り出す技術開発が盛ん
である。例えばC1化学技術が良い例である。石
油化学製品のうちでも、エチレン、プロピレン
は、最も重要な基礎化学品であり年間数百万ｔが
消費されている。このエチレン、プロピレンを石
油以外の炭素資源から製造する方法として合成ガ
スから改良型フイツシヤー・トロプシユ触媒を用
いて製造する方法が検討されているが、エチレ
ン・プロピレン選択性の向上にはシユルツフロー
リ則の制約もあり、多くの困難が存在している。
In recent years, with the depletion of petroleum resources, there has been active development of technology to produce petrochemical products from carbon resources other than petroleum. A good example is C1 chemical technology. Among petrochemical products, ethylene and propylene are the most important basic chemicals, and millions of tons are consumed annually. As a method of producing ethylene and propylene from carbon resources other than petroleum, a method of producing ethylene and propylene from synthesis gas using an improved Fischier-Tropsch catalyst is being considered; However, there are many difficulties.
また、合成ガスから容易に合成することができ
るメタノールからZSM−５等の特異なゼオライ
ト触媒により、エチレン・プロピレを選択的に合
成する方法も見い出されている。しかしこの方法
ではエチレンよりもプロピレンの選択率が多いと
いう欠点がありエチレンを選択的に合成すること
はむづかしい。 Additionally, a method has been discovered to selectively synthesize ethylene and propylene from methanol, which can be easily synthesized from synthesis gas, using a unique zeolite catalyst such as ZSM-5. However, this method has the disadvantage that the selectivity of propylene is higher than that of ethylene, making it difficult to selectively synthesize ethylene.
一方、最近合成ガスから直接エタノールを合成
する触媒も見い出されている。（特開昭58−
141089）
本発明者らは、これらの先行技術をふまえ、ま
たこれらの欠点を克服すべく、合成ガスから一段
でエチレンの選択的合成方法を鋭意検討した結
果、エタノール合成用触媒と特定の脱水素用触媒
を組み合わせた複合系触媒により、合成ガスから
エチレンを選択的に合成するプロセスを見い出す
に至つた。 On the other hand, a catalyst for directly synthesizing ethanol from synthesis gas has recently been discovered. (Unexamined Japanese Patent Publication No. 1983-
141089) Based on these prior art techniques and in order to overcome these drawbacks, the present inventors have intensively investigated a method for selectively synthesizing ethylene from synthesis gas in one step. We have discovered a process for selectively synthesizing ethylene from synthesis gas using a composite catalyst that combines conventional catalysts.
本発明は、複合系触媒により合成ガスから一段
で選択的にエチレンを合成する方法を提供するこ
とを目的としてなされたものである。
The present invention has been made for the purpose of providing a method for selectively synthesizing ethylene from synthesis gas in one step using a composite catalyst.
すなわち、本発明によれば、合成ガスからエタ
ノールを生成する触媒とエタノールを脱水してエ
チレンを生成する触媒を組み合わせ、合成からエ
タノールを合成する反応条件で同時にエタノール
の脱水反応を行い合成ガスから一段で効率良くエ
チレンを生成するプロセスが提供される。
That is, according to the present invention, a catalyst that produces ethanol from synthesis gas and a catalyst that dehydrates ethanol to produce ethylene are combined, and the dehydration reaction of ethanol is simultaneously carried out under the reaction conditions for synthesizing ethanol from the synthesis gas to produce ethylene. provides a process for efficiently producing ethylene.
本発明で用いるエタノール合成用触媒としては
Rhを主活性金属種として含む、一元系あるいは
多元担持Rh触媒であれば任意である。好ましく
は、Rh／SiO2、Rh−Fe／SiO2、Rh−Ti−Fe／
SiO2、Rh−Ti−Fe−Ir／SiO2、Ri−Mn−Fe／
SiO2、等のエタノールの選択率が比較的に高い
ものが良い。 The catalyst for ethanol synthesis used in the present invention is
Any single-component or multi-component supported Rh catalyst containing Rh as the main active metal species may be used. Preferably Rh/ SiO2 , Rh-Fe/ SiO2 , Rh-Ti-Fe/
SiO 2 , Rh-Ti-Fe-Ir/SiO 2 , Ri-Mn-Fe/
It is preferable to use a material with a relatively high selectivity for ethanol, such as SiO 2 .
本発明で用いる脱水触媒としては既存の金属酸
化物あるいはゼオライト等の脱水用酸性物質で良
いが、好ましくはシリカライト、チヤバサイト、
エリオナイト、ゼオロン500H、ゼオロン400Hの
ゼオライトが良い。 The dehydration catalyst used in the present invention may be an existing acidic substance for dehydration such as metal oxide or zeolite, but preferably silicalite, chaabasite,
Zeolites such as Erionite, Zeolon 500H, and Zeolon 400H are good.
本発明で用いる複合触媒系は、上述した触媒を
混合しても良いし、エタノール合成用触媒を上段
に、脱水用触媒を下段に設置しても良い。また両
触媒の割合は任意であるが脱水用触媒が多いほう
が好ましい。 In the composite catalyst system used in the present invention, the above-mentioned catalysts may be mixed, or the ethanol synthesis catalyst may be placed in the upper stage and the dehydration catalyst may be placed in the lower stage. Further, although the ratio of both catalysts is arbitrary, it is preferable that the amount of the dehydration catalyst is large.
本発明の用いる反応条件は合成ガス反応が進行
すれば任意であるが反応温度として100℃〜450
℃、反応圧力1atm〜200Kg／cm2、反応流速として
１ml／min／gCat〜1000ｍ／min／gCat、合成ガ
ス比H2／CO＝10／１〜１／10であれば任意であ
る。好ましくは250℃〜350℃、1atm〜50Kg／cm2、
50ml〜800ml／min、合成ガス比H2／10＝４／１
〜１／４が良い。 The reaction conditions used in the present invention are arbitrary as long as the synthesis gas reaction proceeds, but the reaction temperature is 100°C to 450°C.
C, reaction pressure of 1 atm to 200 Kg/ cm2 , reaction flow rate of 1 ml/min/gCat to 1000 m/min/gCat, and synthesis gas ratio H2 /CO=10/1 to 1/10. Preferably 250℃~350℃, 1atm~50Kg/ cm2 ,
50ml to 800ml/min, synthesis gas ratio H 2 /10 = 4/1
~1/4 is good.
本発明の方法によれば、合成ガスから一段反応
で収良く、エチレンを合成することができるとい
うすぐれた効果を奏する。
According to the method of the present invention, ethylene can be synthesized from synthesis gas in a single step reaction with good yield, which is an excellent effect.
次に本発明を実施例に基づき詳細に説明する。 Next, the present invention will be explained in detail based on examples.
実施例 １
固定床加圧流通式反応装置の反応管（内径８
mm、長さ150mm）の上段にエタノル合成用触媒と
してRh(1)−Fe（0.3）／SiO2（カツコ内は原子比、
Rh4、7wt％）を0.5ｇ、下段に脱水用触媒として
Ｈ−シリカライトを1.5ｇを仕込んだ。合成ガス
反応に先立つてH2気流（300ml／min）中400℃
で1h還元処理を行つた。H2気流中で放冷した後、
室温にて合成ガス（H2／CO＝１）に切り替え反
応温度280℃、反応圧力50Kg／cm2、流速100ml／
minで反応を行つた。反応開始１時間後のCO転
化率は５％であり、生成物の選択率（炭素効率）
はCH448.3％、C2H62.5％、C2H429.3％、C3H80.7
％、C3H62.7％、CH3OH7.0％、C2H5OH0.0％、
C2H5OC2H5微量、C2含酸素化合物5.2％、CO23.3
％、その他1.0％であつた。Example 1 Reaction tube of fixed bed pressurized flow reactor (inner diameter 8
Rh(1)-Fe(0.3)/SiO 2 (atomic ratio in box,
0.5 g of Rh4 (7wt%) and 1.5 g of H-silicalite as a dehydration catalyst were placed in the lower stage. 400℃ in H2 stream (300ml/min) prior to syngas reaction
Reduction treatment was performed for 1 h. After cooling in a stream of H2 ,
Switch to synthesis gas (H 2 /CO = 1) at room temperature, reaction temperature 280℃, reaction pressure 50Kg/cm 2 , flow rate 100ml/
The reaction was carried out at min. The CO conversion rate 1 hour after the start of the reaction was 5%, and the selectivity of the product (carbon efficiency) was
CH4 48.3 % , C2H6 2.5%, C2H4 29.3% , C3H8 0.7
%, C3H6 2.7 %, CH3OH7.0 %, C2H5OH0.0 % ,
C2H5 OC2H5 trace , C2 oxygenates 5.2%, CO2 3.3
%, and others 1.0%.
実施例 ２
固定床加圧流通式反応装置の反応管（内径８
mm、長さ150mm）の上段にエタノル合成用触媒と
してRh(1)−Ti(1)−Fe（0.3）−Ir（0.5）／SiO2（カ
ツコ内は原子比、Rh4、7wt％）を0.5ｇ、下段に
脱水用触媒としてＨ−シリカライトを1.5ｇを仕
込んだ。合成ガス反応に先立つてH2気流（300
ml／min）中400℃で1h還元処理を行つた。H2気
流中で放冷した後、室温にて合成ガス（H2／CO
＝１）に切り替え反応温度260℃、反応圧力50
Kg／cm2、流速100ml／minで反応を行つた。反応
開始１時間後のCO転化率は6.2％であり、生成物
の選択率（炭素効率）はCH432.7％、C2H63.6％、
C2H444.7％、C3H81.2％、C3H62.4％、
CH3OH5.9％、C2H5OH0.0％、C2H5OC2H51.5
％、C2含酸素化合物5.8％、CO23.1％、その他0.6
％であつた。Example 2 Reaction tube of fixed bed pressurized flow reactor (inner diameter 8
mm, length 150 mm) as a catalyst for ethanol synthesis. g, 1.5 g of H-silicalite was charged into the lower stage as a dehydration catalyst. Prior to the synthesis gas reaction, a stream of H2 (300
ml/min) at 400°C for 1 h. After cooling in a H 2 stream, synthesis gas (H 2 /CO
=1) Reaction temperature 260℃, reaction pressure 50
The reaction was carried out at a flow rate of 100 ml/ min at a flow rate of 100 ml/min. The CO conversion rate 1 hour after the start of the reaction was 6.2%, and the product selectivity (carbon efficiency) was 32.7% for CH 4 , 3.6% for C 2 H 6 ,
C2H4 44.7 %, C3H8 1.2%, C3H6 2.4 % ,
CH3OH5.9 % , C2H5OH0.0 % , C2H5OC2H5 1.5
%, C2 oxygenates 5.8%, CO2 3.1%, others 0.6
It was %.
実施例 ３
固定床加圧流通式反応装置の反応管（内径８
mm、長さ150mm）の上段にエタノル合成用触媒と
してRh(1)−Ti(1)−Fe（0.3）−Ir（0.5）／SiO2（カ
ツコ内は原子比、Rh4、7wt％）を0.5ｇ、下段に
脱水用触媒としてゼオロン500Hを1.5ｇを仕込ん
だ。合成ガス反応に先立つてH2気流（300ml／
min）中400℃で1h還元処理を行つた。H2気流中
で放冷した後、室温にて合成ガス（H2／CO＝
１）に切り替え反応温度260℃、反応圧力50Kg／
cm2、流速100ml／minで反応を行つた。反応開始
１時間後のCO転化率は6.1％であり、生成物の選
択率（炭素効率）はCH434.2％、C2H611.9％、
C2H441.9％、C3H81.6％、C3H6微量、CH3OH微
量、C2H5OH0.0％、C2H5OC2H5微量、C2含酸素
化合物 微量、CO210.9％、その他0.3％であつ
た。Example 3 Reaction tube of fixed bed pressurized flow reactor (inner diameter 8
mm, length 150 mm) as a catalyst for ethanol synthesis. g, 1.5 g of Zeolon 500H was charged into the lower stage as a dehydration catalyst. H2 stream (300ml/
Reduction treatment was carried out at 400°C for 1 hour (min). After cooling in a H 2 stream, synthesis gas (H 2 /CO=
Switch to 1) Reaction temperature 260℃, reaction pressure 50Kg/
The reaction was carried out at a flow rate of 100 ml/min at a flow rate of 100 ml/min. The CO conversion rate 1 hour after the start of the reaction was 6.1%, and the product selectivity (carbon efficiency) was 34.2% for CH 4 , 11.9% for C 2 H 6 ,
C 2 H 4 41.9%, C 3 H 8 1.6%, C 3 H 6 trace, CH 3 OH trace, C 2 H 5 OH 0.0%, C 2 H 5 OC 2 H 5 trace, C 2 oxygenated compound trace , CO 2 10.9%, and other 0.3%.
実施例 ４
固定床加圧流通式反応装置の反応管（内径８
mm、長さ150mm）の上段にエタノル合成用触媒と
してRh(1)−Ti(1)−Fe（0.3）−Ir（0.5）／SiO2（カ
ツコ内は原子比、Rh4、7wt％）を0.5ｇ、下段に
脱水用触媒としてゼオロン200Hを1.5ｇを仕込ん
だ。合成ガス反応に先立つてH2気流（300ml／
min）中400℃で1h還元処理を行つた。H2気流中
で放冷した後、室温に合成ガス（H2／CO＝１）
に切り替え反応温度260℃、反応圧力50Kg／cm2、
流速100ml／minで反応を行つた。反応開始１時
間後のCO転化率は6.2％であり、生成物の選択率
（炭素効率）はCH444.8％、C2H65.2％、C2H423.9
％、C3H88.7％、C3H6微量、CH3OH0.2％、
C2H5OH0.0％、C2H5OC2H5微量、C2含酸素化合
物 微量、CO210.9％、その他0.3％であつた。Example 4 Reaction tube of fixed bed pressurized flow reactor (inner diameter 8
mm, length 150 mm) as a catalyst for ethanol synthesis. g, 1.5 g of Zeolon 200H was charged into the lower stage as a dehydration catalyst. H2 stream (300ml/
Reduction treatment was carried out at 400°C for 1 hour (min). After cooling in a stream of H2 , the synthesis gas ( H2 /CO=1) was brought to room temperature.
Switch to reaction temperature 260℃, reaction pressure 50Kg/cm 2 ,
The reaction was carried out at a flow rate of 100 ml/min. The CO conversion rate 1 hour after the start of the reaction was 6.2%, and the product selectivity (carbon efficiency) was CH 4 44.8%, C 2 H 6 5.2%, C 2 H 4 23.9
%, C3H8 8.7 %, C3H6 trace , CH3OH0.2 %,
C 2 H 5 OH 0.0%, C 2 H 5 OC 2 H 5 trace amount, C 2 oxygen-containing compound trace amount, CO 2 10.9%, and others 0.3%.
比較例 １
固定床加圧流通式反応装の反応管（内径８mm、
長さ150mm）の上段にエタノール合成用触媒とし
てRh(1)−Fe（0.3）／SiO2（カツコ内は原子比、
Rh4.7wt％）を0.5ｇ、仕込んだ。合成ガス反応
に先立つてH2気流（300ml／min）中400℃で1h
還元処理を行つた。H2気流中で放冷した後、室
温にて合成ガス（H2／CO＝１）に切り替え反応
温度280℃、反応圧力50Kg／cm2、流速100ml／min
で反応を行つた。反応開始１時間後のCO転化率
は5.0％であり、生成物の選択率（炭素効率）は
CH435.6％、C2H61.4％、C2H40.1％、C3H8.0.2
％、C3H6微量、CH3OH19.8％、C2H5OH32.6％、
C2H5OC2H5微量、C2含酸素化合物39.5％、
CO22.3％、その他1.1％であつた。Comparative Example 1 Reaction tube of fixed bed pressurized flow reactor (inner diameter 8 mm,
Rh(1)-Fe(0.3)/SiO 2 (the atomic ratio in the cutout is
0.5g of Rh4.7wt%) was charged. 1 h at 400 °C in H2 flow (300 ml/min) prior to syngas reaction.
Reduction processing was performed. After cooling in a H 2 stream, switch to synthesis gas (H 2 /CO = 1) at room temperature. Reaction temperature: 280℃, reaction pressure: 50Kg/cm 2 , flow rate: 100ml/min.
I performed the reaction. The CO conversion rate 1 hour after the start of the reaction was 5.0%, and the product selectivity (carbon efficiency) was
CH4 35.6% , C2H6 1.4% , C2H4 0.1 %, C3H8.0.2
%, C3H6 trace , CH3OH19.8 %, C2H5OH32.6 % ,
C2H5 OC2H5 traces , C2 oxygenates 39.5% ,
CO 2 was 2.3% and others 1.1%.
比較例 ２
固定床加圧流通式反応装の反応管（内径８mm、
長さ150mm）の上段にエタノール合成用触媒とし
てRh(1)−Ti(1)−Fe（0.3）Ir（0.5）／SiO2（カツコ
内は原子比、Rh4.7wt％）を0.5ｇ、仕込んだ。
合成ガス反応に先立つてH2気流（300ml／min）
中400℃で1h還元処理を行つた。H2気流中で放冷
した後、室温にて合成ガス（H2／CO＝１）に切
り替え反応温度260℃、反応圧力50Kg／cm2、流速
100ml／minで反応を行つた。反応開始１時間後
のCO転化率は6.3％であり、生成物の選択率（炭
素効率）はCH421.5％、C2H61.3％、C2H40.1％、
C3H80.5％、C3H60.4％、CH3OH3.7％、
C2H5OH50.7％、C2H5OC2H5微量、C2含酸素化
合物65.0％、CO24.2％、その他3.3％であつた。Comparative Example 2 Reaction tube of fixed bed pressurized flow reactor (inner diameter 8 mm,
0.5 g of Rh(1)-Ti(1)-Fe(0.3)Ir(0.5)/SiO 2 (atomic ratio in the cutlet, Rh4.7wt%) was charged into the upper stage (length 150 mm) as a catalyst for ethanol synthesis. is.
H2 stream (300ml/min) prior to synthesis gas reaction
Reduction treatment was performed at 400°C for 1 hour. After cooling in a H 2 stream, switch to synthesis gas (H 2 /CO = 1) at room temperature. Reaction temperature: 260℃, reaction pressure: 50Kg/cm 2 , flow rate.
The reaction was carried out at 100 ml/min. The CO conversion rate 1 hour after the start of the reaction was 6.3%, and the product selectivity (carbon efficiency) was 21.5% for CH 4 , 1.3% for C 2 H 6 , 0.1% for C 2 H 4 ,
C3H8 0.5%, C3H6 0.4 %, CH3OH3.7 % ,
The contents were 50.7% of C2H5OH , trace amounts of C2H5OC2H5 , 65.0% of C2 oxygen - containing compounds, 4.2% of CO2 , and 3.3% of others.
比較例 ３
固定床加圧流通式反応装の反応管（内径８mm、
長さ150mm）の上段にエタノール合成用触媒とし
てRh(1)−Ti(1)−Fe（0.3）Ir（0.5）／SiO2（カツコ
内は原子比、Rh4.7wt％）を0.5ｇ、下段に脱水
用触媒としてγ−Al2O3を1.5ｇを仕込んだ。合成
ガス反応に先立つてH2気流（300ml／min）中
400℃で1h還元処理を行つた。H2気流中で放冷し
た後、室温にて合成ガス（H2／CO＝１）に切り
替え反応温度260℃、反応圧力50Kg／cm2、流速100
ml／minで反応を行つた。反応開始１時間後の
CO転化率は6.2％であり、生成物の選択率（炭素
効率）はCH431.1％、C2H62.0％、C2H47.2％、
C3H80.5％、C3H63.2％、CH3OH4.5％、
C2H5OH17.7％、C2H5OC2H522.4％、C2含酸素化
合物41.1％、CO25.8％、その他4.4％であつた。Comparative Example 3 Reaction tube of fixed bed pressurized flow reactor (inner diameter 8 mm,
0.5 g of Rh(1)-Ti(1)-Fe(0.3)Ir(0.5)/SiO 2 (atomic ratio in the box, Rh4.7wt%) as a catalyst for ethanol synthesis was placed in the upper part (length 150 mm), and in the lower part. 1.5 g of γ-Al 2 O 3 was added as a dehydration catalyst. In H 2 stream (300ml/min) prior to synthesis gas reaction
Reduction treatment was performed at 400°C for 1 hour. After cooling in a H 2 stream, switch to synthesis gas (H 2 /CO = 1) at room temperature. Reaction temperature: 260℃, reaction pressure: 50Kg/cm 2 , flow rate: 100℃.
The reaction was carried out at ml/min. 1 hour after the start of the reaction
The CO conversion rate is 6.2%, and the product selectivity (carbon efficiency) is CH4 31.1%, C2H6 2.0 %, C2H4 7.2 %,
C3H8 0.5%, C3H6 3.2%, CH3OH4.5 % ,
The contents were 17.7% for C 2 H 5 OH, 22.4% for C 2 H 5 OC 2 H 5 , 41.1% for C 2 oxygen-containing compounds, 5.8% for CO 2 , and 4.4% for others.
比較例 ４
固定床加圧流通式反応装の反応管（内径８mm、
長さ150mm）の上段にエタノール合成用触媒とし
てRh(1)−Ti(1)−Fe（0.3）Ir（0.5）／SiO2（カツコ
内は原子比、Rh4.7wt％）を0.5ｇ、下段に脱水
用触媒としてＨ−ZSM−５を1.5ｇを仕込んだ。
合成ガス反応に先立つてH2気流（300ml／min）
中400℃で1h還元処理を行つた。H2気流中で放冷
した後、室温にて合成ガス（H2／CO＝１）に切
り替え反応温度260℃、反応圧力50Kg／cm2、流速
100ml／minで反応を行つた。反応開始１時間後
のCO転化率は6.1％であり、生成物の選択率（炭
素効率）はCH423.3％、C2H61.4％、C2H40.5％、
C3H80.3％、C3H60.7％、CH3OH12.2％、
C2H5OH42.8％、C2H5OC2H5微量、C2含酸素化
合物55.6％、CO23.5％、その他2.6％であつた。Comparative Example 4 Reaction tube of fixed bed pressurized flow reactor (inner diameter 8 mm,
0.5 g of Rh(1)-Ti(1)-Fe(0.3)Ir(0.5)/SiO 2 (atomic ratio in the box, Rh4.7wt%) as a catalyst for ethanol synthesis was placed in the upper part (length 150 mm), and in the lower part. 1.5 g of H-ZSM-5 was charged as a dehydration catalyst.
H2 stream (300ml/min) prior to synthesis gas reaction
Reduction treatment was performed at 400°C for 1 hour. After cooling in a H 2 stream, switch to synthesis gas (H 2 /CO = 1) at room temperature. Reaction temperature: 260℃, reaction pressure: 50Kg/cm 2 , flow rate.
The reaction was carried out at 100 ml/min. The CO conversion rate 1 hour after the start of the reaction was 6.1%, and the product selectivity (carbon efficiency) was 23.3% for CH 4 , 1.4% for C 2 H 6 , 0.5% for C 2 H 4 ,
C3H8 0.3 %, C3H6 0.7 %, CH3OH12.2 %,
The contents were 42.8% C2H5OH , trace amounts of C2H5OC2H5 , 55.6% of C2 oxygen - containing compounds, 3.5% of CO2 , and 2.6% of others.
比較例 ５
固定床加圧流通式反応装の反応管（内径８mm、
長さ150mm）の上段にエタノール合成用触媒とし
てRh(1)−Ti(1)−Fe（0.3）Ir（0.5）／SiO2（カツコ
内は原子比、Rh4.7wt％）を0.5ｇ、下段に脱水
用触媒としてＨ−ZSM−５を1.5ｇを仕込んだ。
合成ガス反応に先立つてH2気流（300ml／min）
中400℃で1h還元処理を行つた。H2気流中で放冷
した後、室温にて合成ガス（H2／CO＝１）に切
り替え反応温度260℃、反応圧力50Kg／cm2、流速
100ml／minで反応を行つた。反応開始0.5時間後
のCO転化率は6.2％であり、生成物の選択率（炭
素効率）はCH466.0％、C2H64.6％、C2H41.8％、
C3H81.1％、C3H62.2％、CH3OH6.5％、
C2H5OH1.4％、C2H5OC2H5微量、C2含酸素化合
物5.1％、CO211.5％、その他1.2％であつた。Comparative Example 5 Reaction tube of fixed bed pressurized flow reactor (inner diameter 8 mm,
0.5 g of Rh(1)-Ti(1)-Fe(0.3)Ir(0.5)/SiO 2 (atomic ratio in the box, Rh4.7wt%) as a catalyst for ethanol synthesis was placed in the upper part (length 150 mm), and in the lower part. 1.5 g of H-ZSM-5 was charged as a dehydration catalyst.
H2 stream (300ml/min) prior to synthesis gas reaction
Reduction treatment was performed at 400°C for 1 hour. After cooling in a H 2 stream, switch to synthesis gas (H 2 /CO = 1) at room temperature. Reaction temperature: 260℃, reaction pressure: 50Kg/cm 2 , flow rate.
The reaction was carried out at 100 ml/min. The CO conversion rate 0.5 hours after the start of the reaction was 6.2%, and the product selectivity (carbon efficiency) was CH 4 66.0%, C 2 H 6 4.6%, C 2 H 4 1.8%,
C3H8 1.1%, C3H6 2.2%, CH3OH6.5 % ,
The contents were 1.4 % C2H5OH , trace amounts of C2H5OC2H5 , 5.1% of C2 oxygen -containing compounds, 11.5% of CO2 , and 1.2% of others.
比較例 ６
固定床加圧流通式反応装の反応管（内径８mm、
長さ150mm）の上段にエタノール合成用触媒とし
てRh(1)−Ti(1)−Fe（0.3）Ir（0.5）／SiO2（カツコ
内は原子比、Rh4.7wt％）を0.5ｇ、下段に脱水
用触媒としてモルデナイトを1.5ｇを仕込んだ。
合成ガス反応に先立つてH2気流（300ml／min）
中400℃で1h還元処理を行つた。H2気流中で放冷
した後、室温にて合成ガス（H2／CO＝１）に切
り替え反応温度260℃、反応圧力50Kg／cm2、流速
100ml／minで反応を行つた。反応開始１時間後
のCO転化率は6.2％であり、生成物の選択率（炭
素効率）はCH450.9％、C2H67.5％、C2H40.0％、
C3H819.7％、C3H60.0％、CH3OH0.0％、
C2H5OH0.0％、C2H5OC2H5微量、C2含酸素化合
物微量、CO215.0％、その他6.9％であつた。Comparative Example 6 Reaction tube of fixed bed pressurized flow reactor (inner diameter 8 mm,
0.5 g of Rh(1)-Ti(1)-Fe(0.3)Ir(0.5)/SiO 2 (atomic ratio in the box, Rh4.7wt%) as a catalyst for ethanol synthesis was placed in the upper part (length 150 mm), and in the lower part. 1.5 g of mordenite was added as a dehydration catalyst.
H2 stream (300ml/min) prior to synthesis gas reaction
Reduction treatment was performed at 400°C for 1 hour. After cooling in a H 2 stream, switch to synthesis gas (H 2 /CO = 1) at room temperature. Reaction temperature: 260℃, reaction pressure: 50Kg/cm 2 , flow rate.
The reaction was carried out at 100 ml/min. The CO conversion rate 1 hour after the start of the reaction was 6.2%, and the product selectivity (carbon efficiency) was CH 4 50.9%, C 2 H 6 7.5%, C 2 H 4 0.0%,
C3H8 19.7 %, C3H6 0.0 %, CH3OH0.0 %,
The contents were 0.0% C 2 H 5 OH, trace amounts of C 2 H 5 OC 2 H 5 , trace amounts of C 2 oxygen-containing compounds, 15.0% CO 2 , and 6.9% of others.
Claims (1)
持多成分系ロジウム触媒とゼオライト触媒を組合
せた複合触媒により、合成ガスから一段でエチレ
ンを選択的に得る方法。1. A method for selectively obtaining ethylene from synthesis gas in one step using a composite catalyst that combines a silica-supported multicomponent rhodium catalyst and a zeolite catalyst to synthesize ethanol from synthesis gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61102471A JPS62258328A (en) | 1986-05-02 | 1986-05-02 | Selective synthesis of ethylene from synthetic gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61102471A JPS62258328A (en) | 1986-05-02 | 1986-05-02 | Selective synthesis of ethylene from synthetic gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62258328A JPS62258328A (en) | 1987-11-10 |
| JPH0468292B2 true JPH0468292B2 (en) | 1992-11-02 |
Family
ID=14328363
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61102471A Granted JPS62258328A (en) | 1986-05-02 | 1986-05-02 | Selective synthesis of ethylene from synthetic gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62258328A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008110302A (en) * | 2006-10-30 | 2008-05-15 | National Institute Of Advanced Industrial & Technology | Catalyst for producing ethylene |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6333342A (en) * | 1986-07-29 | 1988-02-13 | Agency Of Ind Science & Technol | Production of ethylene from synthesis gas |
| JPH0665384B2 (en) * | 1987-12-21 | 1994-08-24 | 日揮株式会社 | Catalyst regeneration method |
| JP2006116439A (en) * | 2004-10-21 | 2006-05-11 | National Institute Of Advanced Industrial & Technology | Catalyst for producing ethylene and method for producing ethylene by using the catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5692825A (en) * | 1979-12-18 | 1981-07-27 | Haldor Topsoe As | Method and catalyst for manufacturing gas mixture containing high quantity of c22hydrocarbons |
| JPS57159723A (en) * | 1981-03-30 | 1982-10-01 | Idemitsu Kosan Co Ltd | Selective preparation of lower unsaturated hydrocarbons |
| JPS60246329A (en) * | 1984-05-21 | 1985-12-06 | Toyota Central Res & Dev Lab Inc | Process for synthesizing hydrocarbon |
| JPS6183134A (en) * | 1984-09-28 | 1986-04-26 | Agency Of Ind Science & Technol | Production of unsaturated hydrocarbon |
-
1986
- 1986-05-02 JP JP61102471A patent/JPS62258328A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5692825A (en) * | 1979-12-18 | 1981-07-27 | Haldor Topsoe As | Method and catalyst for manufacturing gas mixture containing high quantity of c22hydrocarbons |
| JPS57159723A (en) * | 1981-03-30 | 1982-10-01 | Idemitsu Kosan Co Ltd | Selective preparation of lower unsaturated hydrocarbons |
| JPS60246329A (en) * | 1984-05-21 | 1985-12-06 | Toyota Central Res & Dev Lab Inc | Process for synthesizing hydrocarbon |
| JPS6183134A (en) * | 1984-09-28 | 1986-04-26 | Agency Of Ind Science & Technol | Production of unsaturated hydrocarbon |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008110302A (en) * | 2006-10-30 | 2008-05-15 | National Institute Of Advanced Industrial & Technology | Catalyst for producing ethylene |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62258328A (en) | 1987-11-10 |
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