JPH0283038A - Cobalt fischer-tropsch catalyst having improved selectivity - Google Patents
Cobalt fischer-tropsch catalyst having improved selectivityInfo
- Publication number
- JPH0283038A JPH0283038A JP63233877A JP23387788A JPH0283038A JP H0283038 A JPH0283038 A JP H0283038A JP 63233877 A JP63233877 A JP 63233877A JP 23387788 A JP23387788 A JP 23387788A JP H0283038 A JPH0283038 A JP H0283038A
- Authority
- JP
- Japan
- Prior art keywords
- fischer
- molecular sieve
- catalyst
- cobalt
- extracted
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 22
- 239000010941 cobalt Substances 0.000 title claims abstract description 22
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000002808 molecular sieve Substances 0.000 claims abstract description 19
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract 3
- 238000000034 method Methods 0.000 claims 13
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical group [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims 8
- 239000002994 raw material Substances 0.000 claims 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 8
- 150000001336 alkenes Chemical class 0.000 abstract description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- 229910021536 Zeolite Inorganic materials 0.000 abstract 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract 2
- 239000010457 zeolite Substances 0.000 abstract 2
- 229910018404 Al2 O3 Inorganic materials 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000006227 byproduct Substances 0.000 abstract 1
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000011148 porous material Substances 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
PURPOSE: To reduce byproduct methane and to increase the yield of olefins each having carbon atoms of >=5 by combining a cobalt Fischer-Tropsch catalyst with a carrier based on a zeolite molecular sieve. CONSTITUTION: The preparation of this catalyst combined with a molecular sieve carrier, comprises: treating an LZ-2/0 molecular sieve with steam to extract acid from the molecular sieve and to form a TC-123 molecular sieve carrier, wherein the LZ-2/0 molecular sieve is prepared by using a zeolite molecular sieve having an SiO2 /Al2 O3 ratio of >=8.0 as a starting material; and filling the pores of this carrier with a solution of ethylene glycol, water, an alcohol, or the like, which contains Co and an Mn promoter. At the time of performing synthesis gas conversion by using the cobalt Fischer-Tropsch catalyst thus prepared, the methane formation can be reduced and the C5 + yield can be improved.
Description
【発明の詳細な説明】
［産業上の利用分野］
本出願は、改良したモレキュラーシーブ担体と組み合わ
せたコバルトフィッシャー−トロプシュ触媒の分野に関
する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application This application relates to the field of cobalt Fischer-Tropsch catalysts in combination with improved molecular sieve supports.
［従来の技術及び発明が解決しようとする課題１鉄フィ
ッシャー−トロプシュ（Ｆ−Ｔ）触媒は、一般にコバル
トをベースとした触媒以上に商業上好ましいとされてき
ており、現在、使用される唯一の商用Ｆ−Ｔ触媒である
。[Prior Art and Problems to be Solved by the Invention 1 Iron Fischer-Tropsch (F-T) catalysts have generally been commercially preferred over cobalt-based catalysts and are currently the only catalysts in use. It is a commercial FT catalyst.
フィッシャー−トロプシュ反応において合成ガス（ｃｏ
＋ｔ−ｔｇ ）を転化する場合、コバルト触媒は、活性
がより高く及び自動車ガソリンへの選択率が一層良好で
あるという利点を持つが、該触媒は過剰のメタン（望ま
ない生成物）を固有に生成しならびに生成物がパラフィ
ン性であることの悩みがある。もし、メタン生成を減じ
、炭素数５以上の留分（Ｃ５＋）の収率を増加し及びオ
レフィン、特に炭素数５以下（Ｃ５−）の範囲のオレフ
ィンの改善した含有量を示す安定なコバルトＦ−Ｔ触媒
が見出されるならば、重要な触媒の改良になろう。In the Fischer-Tropsch reaction, synthesis gas (co
+t-tg), cobalt catalysts have the advantage of higher activity and better selectivity to motor gasoline, but they inherently remove excess methane (an unwanted product). There are problems with the production and the paraffinic nature of the product. If stable cobalt F reduces methane formation, increases the yield of C5+ fractions (C5+) and shows an improved content of olefins, especially in the C5 or less (C5-) range, If a -T catalyst were found, it would be an important catalyst improvement.
モレキュラーシーブ成分と結合するフィッシャー−トロ
プシュ金属を取り扱った従来技術は、適度な程にある０
本発明に関するもっとも最近の従来技術は、Ｊ、Ａラボ
−（Ｒａｂｏ）らに発行された米国特許第４．６５２．
５３８号の特許及びここに引用する従来技術である。The prior art dealing with Fischer-Tropsch metals combined with molecular sieve components has only moderately
The most recent prior art related to the present invention is U.S. Pat. No. 4.652, issued to J. A. Rabo et al.
'538 patent and the prior art cited herein.
コバルトフィッシャー−トロプシュ触媒に関して過去に
公表された優れた論表はＲ，Ｂアンダーソン（Ａｎｄｅ
ｒｓｏｎ）により［フィッシャー−トロプシュ合成」ア
カデミツクプレス・オーランド（Ｏｒｌａｎｄｏ ）
、フロリダ、１９８４年で報告された。論表の中で、過
去に研究された促進剤及び触媒のリストがあり、Ｍｎ及
びＺｒ促進剤を使用する見解が含まれている０Ｍｎ及び
Ｚｒ促進剤の使゛用に関するこの文献中にある情報の要
約を以下に掲げる。フィッシャーとコツホ（Ｋｏｃｈ）
は、コバルト多孔質ケイソウ上触媒にＭｎを加えると、
本発明における触媒でもまた観測されたように、生成物
の分布をより重質の生成物の方にシフトさせるのに効果
的であることを示した。エイダス（Ｅｉｄｕｓ ）とブ
ラノバ（Ｂｕｌａｎｏｖａ）の研究は、同じタイプの触
媒にＺｒＯ□を添加した際に同様の効果を示したが、こ
れは出願人らのＭｎで促進したＣｏ／ＴＣ−１２３触媒
系へのＺ ｒ Ｏｔの添加では観測されなかった。出願
人らの知る限りにおいては、ＭｎとＺｒとを結合して促
進した触媒を用いるという報告をした研究はない。An excellent previously published paper on cobalt Fischer-Tropsch catalysts is R.B.
[Fischer-Tropsch Synthesis] by Rson, Academic Press Orlando.
, Florida, 1984. In the paper, there is a list of promoters and catalysts that have been studied in the past, and the information in this document regarding the use of Mn and Zr promoters is included, including a discussion of the use of Mn and Zr promoters. A summary is given below. Fisher and Koch
When Mn is added to a cobalt porous diatomaceous catalyst,
It has been shown to be effective in shifting the product distribution towards heavier products, as also observed with the catalyst in the present invention. The work of Eidus and Bulanova showed a similar effect when adding ZrO□ to the same type of catalyst, but this was not the case for Applicants' Mn-promoted Co/TC-123 catalyst system. This was not observed with the addition of Z r Ot to . To the best of Applicants' knowledge, there are no studies reporting the use of catalysts promoted by combining Mn and Zr.
プント（Ｄｅｎｔ） 、 Ａ、 Ｌ及びリン（Ｌｉｎ）
、 Ｍは、Ａｄｖ。Dent, A, L and Lin
, M is Adv.
Claims (16)
ラーシーブにより担持されたコバルトフィッシャー−ト
ロプシュ触媒。(1) Cobalt Fischer-Tropsch catalyst supported on steam-treated, acid-extracted LZ-210 molecular sieves.
２Ｏ＿３比８．０以上を有する請求項１に記載のコバル
トフィッシャー−トロプシュ触媒。(2) Acid-extracted LZ-210 is SiO_2/Al_
The cobalt Fischer-Tropsch catalyst according to claim 1, having a 2O_3 ratio of 8.0 or more.
にて１時間水蒸気処理され、次いで酸抽出された請求項
１に記載のコバルトフィッシャー−トロプシュ触媒。(3) LZ-210 was heated to 750°C in 100% water vapor.
2. The cobalt Fischer-Tropsch catalyst of claim 1, which has been steamed for 1 hour at 100 ml of water and then extracted with acid.
記載のコバルトフィッシャー−トロプシュ触媒。(4) The cobalt Fischer-Tropsch catalyst of claim 1 in combination with an effective amount of a suitable promoter.
バルトフィッシャー−トロプシュ触媒。(5) The cobalt Fischer-Tropsch catalyst according to claim 4, wherein the promoter is manganese oxide.
請求項１に記載の水蒸気処理し、酸抽出したＬＺ−２１
０モレキュラーシーブ担持されたコバルト触媒を使用す
る方法。(6) Steam-treated, acid-extracted LZ-21 according to claim 1 to catalyze the Fischer-Tropsch reaction.
A method using a cobalt catalyst supported on a molecular sieve.
＿２／Ａｌ＿２Ｏ＿３比８．０以上を有する請求項６に
記載の水蒸気処理し、酸抽出したＬＺ−２１０モレキュ
ラーシーブ担持されたコバルト触媒の使用方法。(7) LZ-210 molecular sieve carrier is SiO
7. A method of using the steam-treated, acid-extracted LZ-210 molecular sieve supported cobalt catalyst of claim 6 having a _2/Al_2O_3 ratio of 8.0 or more.
％の水蒸気中で７５０℃にて１時間水蒸気処理され、次
いで酸抽出された請求項６に記載の水蒸気処理し、酸抽
出したＬＺ−２１０モレキュラーシーブ担持されたコバ
ルト触媒の使用方法。(8) LZ-210 molecular sieve carrier is 100
7. The method of using the steam-treated, acid-extracted LZ-210 molecular sieve supported cobalt catalyst of claim 6, wherein the cobalt catalyst is steam-treated and acid-extracted at 750 DEG C. for 1 hour in 50% steam, and then acid-extracted.
ー−トロプシュ反応を触媒する請求項６に記載の水蒸気
処理し、酸抽出したＬＺ−２１０モレキュラーシーブ担
持されたコバルト触媒の使用方法。(9) A method of using the steam-treated, acid-extracted LZ-210 molecular sieve-supported cobalt catalyst of claim 6 for catalyzing the Fischer-Tropsch reaction in combination with an effective amount of a suitable promoter.
ロプシュ反応を触媒する請求項６に記載の水蒸気処理し
、酸抽出したＬＺ−２１０モレキュラーシーブ担持され
たコバルト触媒の使用方法。(10) The method of using the steam-treated, acid-extracted LZ-210 molecular sieve-supported cobalt catalyst according to claim 6, wherein the promoter is manganese oxide to catalyze the Fischer-Tropsch reaction.
シュ反応を実施する方法であって、上記原料流を、適当
なフィッシャー−トロプシュ反応条件で、コバルトおよ
び水蒸気処理し酸抽出したＬＺ−２１０モレキュラーシ
ーブ担体を含む触媒に接触させることを含む上記方法。(11) A method of carrying out a Fischer-Tropsch reaction using a raw material stream of synthesis gas, wherein the raw material stream is treated with cobalt and steam and acid-extracted with an LZ-210 molecular sieve carrier under appropriate Fischer-Tropsch reaction conditions. The above method comprising contacting a catalyst comprising:
Ｏ＿２／Ａｌ＿２Ｏ＿３比８．０以上を有する請求項１
１に記載のフィッシャー−トロプシュ反応の実施方法。(12) LZ-210 molecular sieve carrier is Si
Claim 1 having an O_2/Al_2O_3 ratio of 8.0 or more
1. A method for carrying out the Fischer-Tropsch reaction as described in 1.
０％の水蒸気中で７５０℃にて１時間水蒸気処理され、
次いで酸抽出されている請求項１１に記載のフィッシャ
ー−トロプシュ反応を実行する方法。(13) LZ-210 molecular sieve carrier has 10
Steam treated at 750°C for 1 hour in 0% steam,
12. A method for carrying out a Fischer-Tropsch reaction according to claim 11, which is then acid extracted.
求項１１に記載の合成ガスの原料流によるフィッシャー
−トロプシュ反応の実施方法。14. The method of carrying out a Fischer-Tropsch reaction with a feed stream of synthesis gas as claimed in claim 11, wherein the catalyst also comprises an effective amount of a suitable promoter.
項１４に記載のフィッシャー−トロプシュ反応の実施方
法。(15) The method of carrying out the Fischer-Tropsch reaction according to claim 14, wherein the catalyst also comprises a manganese oxide promoter.
シュ反応を実施する方法であって、上記原料流を、適当
なフィッシャー−トロプシュ反応条件下で、コバルトお
よび水蒸気処理し酸抽出したＬＺ−２１０モレキュラー
シーブを酸化マンガンと組み合わせて含む触媒に接触さ
せることを含む方法。(16) A method of carrying out a Fischer-Tropsch reaction using a feed stream of synthesis gas, wherein the feed stream is treated with cobalt and steam and acid-extracted with LZ-210 molecular sieves under appropriate Fischer-Tropsch reaction conditions. A method comprising contacting a catalyst comprising in combination with manganese oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63233877A JPH0283038A (en) | 1988-09-20 | 1988-09-20 | Cobalt fischer-tropsch catalyst having improved selectivity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63233877A JPH0283038A (en) | 1988-09-20 | 1988-09-20 | Cobalt fischer-tropsch catalyst having improved selectivity |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0283038A true JPH0283038A (en) | 1990-03-23 |
Family
ID=16961966
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63233877A Pending JPH0283038A (en) | 1988-09-20 | 1988-09-20 | Cobalt fischer-tropsch catalyst having improved selectivity |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0283038A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5473177A (en) * | 1990-11-16 | 1995-12-05 | Sumitomo Electric Industries, Ltd. | Field effect transistor having a spacer layer with different material and different high frequency characteristics than an electrode supply layer thereon |
| JP2011063811A (en) * | 2003-01-31 | 2011-03-31 | Chevron Usa Inc | High purity olefinic naphtha for production of ethylene and propylene |
| JP2013511591A (en) * | 2009-11-20 | 2013-04-04 | シェブロン ユー．エス．エー． インコーポレイテッド | Cobalt supported zeolite hybrid Fischer-Tropsch catalyst |
| WO2015080611A1 (en) | 2013-11-26 | 2015-06-04 | Infra XTL Technology Limited | Catalyst for direct production of isoparaffin-rich synthetic oil and method for preparing catalyst |
| JP2021520992A (en) * | 2018-04-13 | 2021-08-26 | ハイケム株式会社 | A method for producing a catalyst used when synthesizing aviation kerosene from syngas, a catalyst obtained by the method, and its use. |
-
1988
- 1988-09-20 JP JP63233877A patent/JPH0283038A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5473177A (en) * | 1990-11-16 | 1995-12-05 | Sumitomo Electric Industries, Ltd. | Field effect transistor having a spacer layer with different material and different high frequency characteristics than an electrode supply layer thereon |
| JP2011063811A (en) * | 2003-01-31 | 2011-03-31 | Chevron Usa Inc | High purity olefinic naphtha for production of ethylene and propylene |
| JP2013511591A (en) * | 2009-11-20 | 2013-04-04 | シェブロン ユー．エス．エー． インコーポレイテッド | Cobalt supported zeolite hybrid Fischer-Tropsch catalyst |
| WO2015080611A1 (en) | 2013-11-26 | 2015-06-04 | Infra XTL Technology Limited | Catalyst for direct production of isoparaffin-rich synthetic oil and method for preparing catalyst |
| JP2021520992A (en) * | 2018-04-13 | 2021-08-26 | ハイケム株式会社 | A method for producing a catalyst used when synthesizing aviation kerosene from syngas, a catalyst obtained by the method, and its use. |
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