JPS6323742A - Reduction catalyst - Google Patents
Reduction catalystInfo
- Publication number
- JPS6323742A JPS6323742A JP62147320A JP14732087A JPS6323742A JP S6323742 A JPS6323742 A JP S6323742A JP 62147320 A JP62147320 A JP 62147320A JP 14732087 A JP14732087 A JP 14732087A JP S6323742 A JPS6323742 A JP S6323742A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- carrier
- cobalt
- gas
- iron
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 24
- 239000010941 cobalt Substances 0.000 claims abstract description 21
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052742 iron Inorganic materials 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 13
- 239000001257 hydrogen Substances 0.000 abstract description 13
- 229910000428 cobalt oxide Inorganic materials 0.000 abstract description 5
- 230000002829 reductive effect Effects 0.000 abstract description 5
- -1 for example Substances 0.000 abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 46
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 229930195733 hydrocarbon Natural products 0.000 description 10
- 150000002430 hydrocarbons Chemical class 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 239000000571 coke Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910002651 NO3 Inorganic materials 0.000 description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 229910052707 ruthenium Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 229910002090 carbon oxide Inorganic materials 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 229910001960 metal nitrate Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- 229910019891 RuCl3 Inorganic materials 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 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
Abstract
Description
【発明の詳細な説明】
本発明は水素及び−酸化炭素を含むガス、あるいは更に
二酸化炭素を含む低カロリーガスから炭素数１〜４の炭
化水素を含む高カロリーガスを製造するための触媒に関
するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a catalyst for producing a high-calorie gas containing a hydrocarbon having 1 to 4 carbon atoms from a gas containing hydrogen and carbon oxide, or a low-calorie gas containing carbon dioxide. It is.
都市ガスとしては、従来、コークス炉ガスが主流を占め
てきたが、近年生活環境の保護、供給方式の合理化、無
毒安全性等の観点から見直しが行なわれ、高カロリー天
然ガスへの転換が急ピッチで進められている。そのため
コークス炉ガスは都市ガスとしての用途をせばめられつ
つあるが、製鉄用コークスの生産に伴って膨大な量が副
生ずるので、この有用な用途を開発することが重要な課
題になりている。ところでこのコークス炉ガスを今後と
も燃料用として活用していくためには現在の低カロリー
性を改善し、天然ガスに匹敵し得る様な高カロリーガス
に変換することが必要である。Traditionally, coke oven gas has been the mainstream source of city gas, but in recent years it has been reviewed from the viewpoints of protecting the living environment, rationalizing supply methods, non-toxic safety, etc., and there is a sudden shift to high-calorie natural gas. Things are progressing on the pitch. For this reason, the use of coke oven gas as a city gas is being limited, but since a huge amount is produced as a by-product in the production of coke for steelmaking, it is important to develop useful uses for this gas. However, in order to continue to utilize this coke oven gas as a fuel, it is necessary to improve its current low calorie property and convert it into a high calorie gas comparable to natural gas.
代替天然ガス（以下ＳＮＧという）の製造法としては、
石炭系責源からのガス、例えば石炭ガス化ガスからメタ
ンを合成するか、またはコークス炉ガスに高価なナフサ
やＬＰＧを添加し接触改質してメタン化する方法等が提
案されている。ここで得られる、メタン主体のＳＮＧは
せいぜい８．５００ ｋｃａｌ／Ｎｍ’ないしそれ以下
のカロリーを有するに過ぎず、天然ガスなみの都市ガス
として供給するためにはＬＰＧ等を添加して増熱する必
要がある。本発明者等は上述の事情に鑑み、種々研究の
結果水素および一酸化炭素を含むガス、あるいは更に二
酸化炭素を含むガス（以下、単に低カロリーガスと称す
）例えばコークス炉ガスを高カロリーガスに変換するこ
とのできる三元組成系触媒を見出し、先にその製造方法
につき特許出願を行った（特開昭５９−４６１３３号）
。The production method for alternative natural gas (hereinafter referred to as SNG) is as follows:
Proposed methods include synthesizing methane from gas from coal-based sources, such as coal gasified gas, or adding expensive naphtha or LPG to coke oven gas and catalytically reforming it to produce methane. The methane-based SNG obtained here has a calorie of at most 8.500 kcal/Nm' or less, and in order to supply it as city gas comparable to natural gas, it must be heated by adding LPG, etc. There is a need. In view of the above-mentioned circumstances, the present inventors have conducted various studies to convert gases containing hydrogen and carbon monoxide, or gases further containing carbon dioxide (hereinafter simply referred to as low-calorie gases), such as coke oven gas, to high-calorie gases. He discovered a ternary composition catalyst that could perform the conversion, and filed a patent application for its manufacturing method (Japanese Patent Application Laid-Open No. 59-46133).
.
すなわち、同出願の発明はシリカおよび／またはアルミ
ナよりなる担体に、触媒基質としての鉄および／または
コバルトにマンガン酸化物と白金族金属とを組合わせて
担持させてなる触媒に上記低カロリーガスを接触させる
と、メタンのほか、□炭素数が２〜４の炭化水素をも含
む高カロリーガスに変換することができるというもので
ある。That is, the invention of the same application applies the above-mentioned low-calorie gas to a catalyst in which a combination of manganese oxide and platinum group metal is supported on iron and/or cobalt as a catalyst substrate on a carrier made of silica and/or alumina. When brought into contact, it can be converted into a high-calorie gas containing not only methane but also hydrocarbons having 2 to 4 carbon atoms.
本発明者等は、上記三元組成系触媒の高カロリーガス生
成性能を向上させるため、さらに検討をすすめたところ
、触媒基質としての鉄および／またはコバルトの担持量
を、担体を含む全触媒重量に対して５％を超え２５％以
下に調製したところ、触媒寿命が改善されることを見出
し本発明を完成した。尚この触媒を製造する方法につい
ては一切限定されないが、特に好ましいのは、シリカお
よび／またはアルミナよりなる担体に、まず、白金族金
属を担持させ、ついで鉄および／またはコバルトと酸化
マンガンを同時に担持させて三元組成系触媒を得、次い
で還元性７囲気下５００〜９５０℃の温度で熱処理する
方法であり、これによって耐熱性および触媒寿命の長い
ものが得られる。以下、本発明をさらに詳細に説明する
。In order to improve the high-calorie gas generation performance of the above-mentioned ternary composition catalyst, the present inventors conducted further studies and found that the amount of iron and/or cobalt supported as a catalyst substrate was determined by the total catalyst weight including the carrier. The present invention was completed by discovering that the life of the catalyst was improved when the content of the catalyst was adjusted to more than 5% and less than 25%. The method for producing this catalyst is not limited at all, but it is particularly preferable to first support a platinum group metal on a carrier made of silica and/or alumina, and then simultaneously support iron and/or cobalt and manganese oxide. This is a method of obtaining a ternary composition catalyst, which is then heat-treated at a temperature of 500 to 950°C under a reducing atmosphere, thereby obtaining a catalyst with long heat resistance and catalyst life. The present invention will be explained in more detail below.
本発明において触媒成分の担持される触媒担体は、一般
に市販されたいるシリカまたはアルミナであり、例えば
シリカ担体の場合、比表面積が５００ｍ’／ｇ以下のも
の、またアルミナ担体の場合、比表面積が３８０ｍ’／
ｇ以下のものが好ましい。なおこれら担体は触媒成分の
担持と、反応ガス（未反応ガスと生成ガス）の拡散を改
善する目的で、触媒成分を担持させるに当って、あらか
じめ５００〜１１００℃の温度で熱処理しておくことが
好ましい。In the present invention, the catalyst carrier on which the catalyst component is supported is generally commercially available silica or alumina. For example, a silica carrier has a specific surface area of 500 m'/g or less, and an alumina carrier has a specific surface area of 500 m'/g or less. 380m'/
g or less is preferable. In addition, these carriers should be heat-treated at a temperature of 500 to 1100°C in advance to support the catalyst components for the purpose of supporting the catalyst components and improving the diffusion of the reaction gas (unreacted gas and generated gas). is preferred.
上記のような担体に担持させる触媒成分の基質としては
鉄および／またはコバルトが用いられる。そしてこの基
質金属にマンガン酸化物および白金族金属（例えばルテ
ニウム、ロジウム、パラジウム、白金、およびイリジウ
ム等）を組み合わせて前記担体上に担持させたものであ
る。Iron and/or cobalt is used as a substrate for the catalyst component supported on the carrier as described above. This substrate metal is combined with a manganese oxide and a platinum group metal (for example, ruthenium, rhodium, palladium, platinum, iridium, etc.) and supported on the carrier.
上記組み合わせにおいて、触媒基質となる鉄および／ま
たはコバルトの担持量は全触媒に対し１５％を超え２５
％以下と定める。これは１５％を超えることによって触
媒寿命が長くなるからであり、２５％を超えて担持させ
ることは噴霧法を採用するにしても技術的に困難を伴う
。酸化マンガンの担持量は特に制限されないが、鉄およ
び／またはコバルト元素対マンガン元素の原子比が（５
： １ ）〜（５：４）の範囲を満足するように設定す
るのが良い。白金族金属の担持量も限定されないが、鉄
および／またはコバルト元素対白金族金属の原子比が（
３０：１）〜（５：２）の範囲を満足するように設定す
るのが好ましい。In the above combination, the supported amount of iron and/or cobalt as a catalyst substrate exceeds 15% of the total catalyst.
% or less. This is because the life of the catalyst becomes longer when the content exceeds 15%, and it is technically difficult to support more than 25% even if a spraying method is employed. The amount of manganese oxide supported is not particularly limited, but the atomic ratio of iron and/or cobalt elements to manganese elements is (5
:1) to (5:4). The amount of platinum group metal supported is also not limited, but the atomic ratio of iron and/or cobalt elements to platinum group metal is (
It is preferable to set the ratio to satisfy the range of 30:1) to 5:2.
すなわち、触媒を調製するに当っては、上記シリカおよ
び／またはアルミナよりなる担体に、たとえばまず白金
族金属を担持させ、ついで鉄および／またはコバルトと
酸化マンガンとを同時に担持させて得られた三元組成系
触媒を還元性罪囲気例えば水素の存在下５００〜９５０
℃の温度で熱処理する。なお、前記手順にしたがフて得
られる触媒は、前記以外の方法、例えば鉄および／また
はコバルトと酸化マンガンを先に担持させ、そのあとで
白金族金属を担持させて得られる触媒、白金族金属と酸
化マンガンと鉄および／またはコバルトを同時に担持さ
せて得られる触媒および金属触媒を担持させたあと、上
記温度範囲外で熱処理して得られる触媒などとくらべて
、低カロリーガスを炭素数２〜４の炭化水素をも含有す
る高カロリーガスに変換する能力がはるかに有効に発揮
されることが本発明者等によって確認されたが、本発明
の触媒はその製造手順によって技術的範囲が制限される
訳ではない。本発明の触媒は、具体的にはシリカおよび
／またはアルミナよりなる担体に、鉄および／またはコ
バルト、マンガンおよび白金族金属をそれぞれ硝酸塩水
溶液または塩化物水溶液の形で噴震、散布、浸漬等の手
段により含浸させたあと、乾燥、アンモニア処理、熱分
解、還元等の工程を順次流して製造される。尚これに最
終工程としての熱処理を施すことにより更に良い結果、
即ち長寿命触媒が得られる。なお、この調製にあたり、
アンモニア処理工程は省略できる場合もある。本発明の
触媒の製造例をさらに具体的に説明する。That is, in preparing a catalyst, for example, a platinum group metal is first supported on the carrier made of silica and/or alumina, and then iron and/or cobalt and manganese oxide are simultaneously supported. The original composition of the catalyst is reduced to 500 to 950 in the presence of hydrogen, for example.
Heat treatment at a temperature of °C. Note that the catalyst obtained by following the above procedure may be obtained by a method other than the above, such as a catalyst obtained by first supporting iron and/or cobalt and manganese oxide, and then supporting a platinum group metal, or a catalyst obtained by supporting a platinum group metal after that. Compared to catalysts obtained by simultaneously supporting metals, manganese oxide, iron and/or cobalt, and catalysts obtained by supporting metal catalysts and then heat-treating them outside the above temperature range, low-calorie gases with a carbon number of 2 Although the present inventors have confirmed that the ability to convert ~4 hydrocarbons into high-calorie gas containing them is much more effective, the technical range of the catalyst of the present invention is limited by its manufacturing procedure. That doesn't mean it will happen. Specifically, the catalyst of the present invention is prepared by applying iron and/or cobalt, manganese, and platinum group metals to a carrier made of silica and/or alumina in the form of a nitrate aqueous solution or a chloride aqueous solution, respectively, by squirting, spraying, immersing, etc. After being impregnated by means, it is manufactured by sequentially performing steps such as drying, ammonia treatment, thermal decomposition, and reduction. Furthermore, by applying heat treatment as the final step, even better results can be obtained.
That is, a long-life catalyst can be obtained. In addition, for this preparation,
In some cases, the ammonia treatment step can be omitted. A manufacturing example of the catalyst of the present invention will be explained in more detail.
まず、シリカおよび／またはアルミナよりなる担体また
はこれを５００〜１１００℃で熱処理した担体に、その
細孔容積と等量の白金族金属硝酸塩または同塩化物の水
溶液を含浸させ、常温でゆるやかに担体を転勤させなが
ら風乾する。なお、この乾燥操作は温度ｔＳＯ℃までの
乾燥器内で行ってもよい。つぎに上記処理物を、１０〜
１１容量％アンモニアガスと２〜６容量％水蒸気を含む
雰囲気中に２〜３分間曝露する。その後、空気中で約３
５０℃まで加熱し、含浸されている白金族金属硝酸塩ま
たは同塩化物を分解して酸化物とする。これを不活性ガ
スで希釈した水素濃度１０〜２０容量％の気流中で４０
０℃まで昇温し同温度で３０分間保持して還元し、再び
同気流中で常温まで冷却する。このようにして得られた
白金族金属担持体に前記と同じ含浸法により、鉄および
／またはコバルト例えば硝酸塩水溶液と、マンガンの例
えば硝酸塩水溶液との混合溶液を含浸させる。ついで前
記白金族金属を担持させる場合と同様に風乾、アンモニ
ア処理、熱分解、水素還元等の操作を施して三元組成系
触媒を調製する。First, a carrier made of silica and/or alumina or a carrier heat-treated at 500 to 1100°C is impregnated with an aqueous solution of a platinum group metal nitrate or chloride in an amount equal to the pore volume of the carrier, and the carrier is slowly heated at room temperature. Air dry while transferring. Note that this drying operation may be performed in a dryer at a temperature of tSO°C. Next, the above-mentioned treated product was added to
Exposure for 2-3 minutes to an atmosphere containing 11% by volume ammonia gas and 2-6% by volume water vapor. Then, in the air about 3
It is heated to 50°C to decompose the impregnated platinum group metal nitrate or chloride into an oxide. This was diluted with an inert gas for 40 minutes in an air stream with a hydrogen concentration of 10 to 20% by volume.
The temperature is raised to 0°C, maintained at the same temperature for 30 minutes for reduction, and cooled again to room temperature in the same air flow. The platinum group metal support thus obtained is impregnated with a mixed solution of an aqueous solution of iron and/or cobalt, such as a nitrate, and an aqueous solution of manganese, such as a nitrate, by the same impregnation method as described above. Then, as in the case of supporting the platinum group metal, operations such as air drying, ammonia treatment, thermal decomposition, and hydrogen reduction are performed to prepare a ternary composition catalyst.
つぎに、これを還元性雰囲気例えば１００％水素気流中
１〜３時間を要して常温から５００〜９５０℃に昇温し
、同温度で保持して熱処理を行い、そのあと同気流中で
常温まで冷却する。この熱処理において、処理温度が５
００℃よりも低いと炭素数２〜４の炭化水素の生成量が
低く、また９５０℃より高いと一酸化炭素転化活性が低
下するので好ましくない。又熱処理時間については特に
制限はないが、１０分〜５時間とすることが好ましく、
より好ましくは３０分〜２時間である。このような熱処
理を施すと耐熱性にとみ、寿命のより長い触媒が得られ
るとともに、これに低カロリーガスを接触させた場合、
炭素数が２〜４の炭化水素をより多く含有する高カロリ
ーガスが得られるという利点があり、その経済的効果は
絶大である。Next, the temperature is raised from room temperature to 500 to 950°C over a period of 1 to 3 hours in a reducing atmosphere, for example, a 100% hydrogen stream, and heat treatment is performed by keeping it at the same temperature. Cool until cool. In this heat treatment, the treatment temperature was 5
If the temperature is lower than 00°C, the amount of hydrocarbons having 2 to 4 carbon atoms produced will be low, and if it is higher than 950°C, the carbon monoxide conversion activity will decrease, which is not preferable. There is no particular restriction on the heat treatment time, but it is preferably 10 minutes to 5 hours.
More preferably, the time is 30 minutes to 2 hours. By applying such heat treatment, a catalyst with improved heat resistance and longer life can be obtained, and when brought into contact with a low-calorie gas,
There is an advantage that a high-calorie gas containing a larger amount of hydrocarbons having 2 to 4 carbon atoms can be obtained, and its economic effect is enormous.
なお、このような効果が得られるのは次のような理由に
よるものと推定される。すなわち、触媒基質である鉄お
よび／またはコバルトがシンタリングによって適当な大
きさの粒子に成長すると共に水素吸着速度が減少し、し
たがって−酸化炭素のメタン化活性は低下するが、吸着
−酸化炭素の活性表面での滞留時間が増すため、炭素重
合が促進され、炭素数２〜４の炭化水素の生成が向上す
る。In addition, it is presumed that the reason why such an effect is obtained is as follows. That is, as the catalyst substrate iron and/or cobalt grows into particles of appropriate size through sintering, the hydrogen adsorption rate decreases, and therefore the methanation activity of carbon oxide decreases, but the adsorption rate of carbon oxide decreases. The increased residence time on the active surface promotes carbon polymerization and improves the production of C2-C4 hydrocarbons.
本発明の触媒によって、コークス炉ガス、ナフサや重質
油の水蒸気改質ガス更には水性ガスや石炭ガス化ガスの
ような低カロリーガスを炭素数１〜４の炭化水素を含む
高カロリーガスに変換するには、例えばつぎのようにし
て行なうことができる。すなわち、以上のようにして得
られた触媒を反応塔に充填し、触媒層の温度を１５０〜
４００℃、好ましくは２００〜３５０℃に制御しながら
５〜３０ｋｇ／ｃｍ２：ゲージ圧（以下Ｇと表わす）
、好ましくは１０〜２０ｋｇ／ｃｍ２Ｇの加圧下に、触
媒容量１１当り１〜１０ｍ３／ｈｒ 、好ましくは２〜
５ ｍ’／ｈｒの低カロリーガスを導入することにより
触媒層内で、炭素数が１〜４の炭化水素を含有する高カ
ロリーガスが生成する。尚シフト反応等によって若干副
生ずるＣＯ２はＰＳＡ法等によって除去すれば良い。By using the catalyst of the present invention, low-calorie gases such as coke oven gas, steam-reformed gas of naphtha and heavy oil, as well as water gas and coal gasification gas are converted into high-calorie gas containing hydrocarbons having 1 to 4 carbon atoms. For example, the conversion can be performed as follows. That is, the catalyst obtained as described above is packed into a reaction tower, and the temperature of the catalyst layer is set to 150~150℃.
5 to 30 kg/cm2: Gauge pressure (hereinafter referred to as G) while controlling at 400°C, preferably 200 to 350°C
, preferably under a pressure of 10 to 20 kg/cm2G, per 11 catalyst capacities, 1 to 10 m3/hr, preferably 2 to
By introducing the low calorie gas at a rate of 5 m'/hr, a high calorie gas containing hydrocarbons having 1 to 4 carbon atoms is generated in the catalyst layer. Incidentally, CO2 produced as a by-product due to the shift reaction may be removed by a PSA method or the like.
以下本発明を実施例によって説明するが、本発明はその
要旨を越えない限り、下記実施例に限定されることはな
い。なお説明中「部」とあるは重量部を表わす。The present invention will be explained below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. In the description, "parts" represent parts by weight.
実施例１
比表面積約２００ｍ’／ｇの市販アルミナ担体を、空気
中において常温から１０６０℃まで４〜５時間で昇温し
、同温度で３０分間保持し、被熱処理担体を得た。この
担体２０部に、ＲｕＣｌ３ ・３Ｈ２００，１部を水
５．０部に溶解させた水溶液を噴ｎ法により含浸させ、
ついで、ゆるやかに転勤させながら一夜風乾し含浸物を
得た。この含浸物をあらかじめ１０〜１１容量％のアン
モニアと６容量％水蒸気となる霊囲気に２０℃で２分間
曝露し、ついで空気中で約３５０℃まで加熱してルテニ
ウム金属塩を熱分解して酸化物とした。これを電気炉に
入れて水素濃度２０容量％の窒素気流を導通しながら常
温から４００℃まで１時間で昇温し、その温度で３０分
間保持することによってルテニウム金属酸化物を還元し
てから、同気流中で常温まで冷却し、ルテニウム担持触
媒を得た。このルテニウム担持触媒にＣｏ （ＮＯ３）
２ ・６Ｈ２０２６，２部およびＭｎ（ＮＯ３） ２
・６Ｈ２０６，１部を水５．０部に溶解させた溶液を前
記ＲｕＣｌ３ ・３Ｈ２０含浸の場合と同様の操作法
で含浸させ、同様の条件で乾燥、熱分解および還元処理
を行い、コバルト、酸化マンガン（Ｍｎ２０３ ）およ
びルテニウムを担持させた三元組成系触媒を得た。つぎ
に該三元組成系触媒を１００％水素気流中常温から８５
０℃まで１〜３時間を要して昇温し、そ−の温度で３０
分間保持して熱処理を行い、同気流中で常温まで冷却し
、組成割合が２０％Ｃｏ−１２％Ｍｎ２Ｏ３−０，１％
Ｒｕからなる三元組成系触媒２６．５部を得た。この触
媒上へ第１表に示す組成よりなる低カロリーの供試ガス
を圧力１０ｋｇ／ｃｍ２Ｇ 、 Ｓ Ｖ ２５００ｈ
ｒ−’、温度２６０℃で１回通過させたところ、ｃ。Example 1 A commercially available alumina carrier having a specific surface area of about 200 m'/g was heated in air from room temperature to 1060°C over 4 to 5 hours, and held at the same temperature for 30 minutes to obtain a heat-treated carrier. 20 parts of this carrier was impregnated with an aqueous solution in which 1 part of RuCl3.3H200 was dissolved in 5.0 parts of water by the spray method.
Then, the impregnated material was obtained by air-drying it overnight while gently transferring it. This impregnated material was previously exposed to ashes containing 10 to 11% by volume of ammonia and 6% by volume of water vapor at 20°C for 2 minutes, and then heated in air to approximately 350°C to thermally decompose and oxidize the ruthenium metal salt. It became a thing. This was placed in an electric furnace, and the temperature was raised from room temperature to 400°C in 1 hour while passing a nitrogen stream with a hydrogen concentration of 20% by volume, and the ruthenium metal oxide was reduced by holding at that temperature for 30 minutes. The mixture was cooled to room temperature in the same air flow to obtain a ruthenium-supported catalyst. Co (NO3) is added to this ruthenium supported catalyst.
2 ・6H2026, 2 parts and Mn(NO3) 2
・A solution prepared by dissolving 1 part of 6H206 in 5.0 parts of water was impregnated in the same manner as in the RuCl3 ・3H20 impregnation, and dried, thermally decomposed and reduced under the same conditions to remove cobalt, oxidized A ternary composition catalyst supporting manganese (Mn203) and ruthenium was obtained. Next, the ternary composition catalyst was heated to 85°C from room temperature in a 100% hydrogen stream.
It takes 1 to 3 hours to raise the temperature to 0℃, and at that temperature it is heated for 30 minutes.
Heat treatment is performed by holding for a minute, and then cooled to room temperature in the same air flow, and the composition ratio is 20%Co-12%Mn2O3-0.1%
26.5 parts of a ternary composition catalyst consisting of Ru was obtained. A low calorie test gas having the composition shown in Table 1 was poured onto this catalyst at a pressure of 10 kg/cm2G and an SV of 2500 h.
r-', after one pass at a temperature of 260°C, c.
転化率１００％で第３表に示す組成よりなる高カロリー
のガスを得た。A high-calorie gas having the composition shown in Table 3 was obtained at a conversion rate of 100%.
第１表
実施例２
比表面積的５００ｍ’／ｇの市販シリカ担体を空気中に
おいて常温からａｏｏｔまで４〜６時間で昇温し、同温
度で３０分間保持して被熱処理担体を得た。ついでＲｕ
Ｃｌ３ ・３Ｈ２０２，５部を水５．０部に溶解して得
た水溶液を、噴震法により上記被熱処理担体２０部に含
浸させ、ついで、ゆるやかに転勤させながら一夜風乾し
、含浸物を得た。この含浸物をあらかじめ１０〜１１容
量％のアンモニアと６容量％の水蒸気を含む雰囲気に２
０℃で２分間曝露し、ついで空気中において約３５０℃
まで加熱してルテニウム金属塩を熱分解した。これを電
気炉に入れ、水素濃度２０容量％の窒素気流を導通しな
がら常温から４００℃まで１時間で昇温し、その温度で
３０分間保持してルテニウム金属酸化物を還元してから
同気流中で常温まで冷却し、ルテニウム担持触媒を得た
。ついでＦｅ （ＮＯ３）２ ・９Ｈ２０４０，５部お
よびＭｎ （ＮＯ３）２ ・６Ｈ２０６，４部を水５．
０部に溶解した溶液を、前記ＲｕＣｌ３ ・３Ｈ２０
を含浸させる場合と同様の操作法で上記ルテニウム担持
触媒に含浸させ、同様の条件で乾燥、熱分解および還元
処理を行い、コバルト、酸化マンガン（Ｍｎ２０ａ ）
およびルテニウムを担持させた三元組成系触媒を得た。Table 1 Example 2 A commercially available silica carrier having a specific surface area of 500 m'/g was heated in air from room temperature to aoot over 4 to 6 hours and held at the same temperature for 30 minutes to obtain a heat-treated carrier. Then Ru
An aqueous solution obtained by dissolving 202.5 parts of Cl3.3H in 5.0 parts of water was impregnated into 20 parts of the above-mentioned heat-treated carrier by the jetting method, and then air-dried overnight while being gently transferred to obtain an impregnated product. Ta. This impregnated material was placed in advance in an atmosphere containing 10 to 11% by volume of ammonia and 6% by volume of water vapor.
Exposure for 2 minutes at 0°C, then approximately 350°C in air
The ruthenium metal salt was thermally decomposed by heating to . This was placed in an electric furnace, and the temperature was raised from room temperature to 400°C in 1 hour while passing a nitrogen stream with a hydrogen concentration of 20% by volume, and the temperature was held at that temperature for 30 minutes to reduce the ruthenium metal oxide, after which the same air stream was passed through. The mixture was cooled to room temperature to obtain a ruthenium-supported catalyst. Next, 5 parts of Fe (NO3)2 .9H2040 and 4 parts of Mn (NO3)2 .6H206 were added to 5.0 parts of water.
The solution dissolved in 0 parts of RuCl3.3H20
Cobalt, manganese oxide (Mn20a) was impregnated into the ruthenium-supported catalyst using the same procedure as in the case of impregnating cobalt, manganese oxide (Mn20a), and dried, thermally decomposed and reduced under the same conditions.
And a ternary composition catalyst supporting ruthenium was obtained.
つぎに該三元組成系触媒を１０．０９４水素気流中、常
温から７００℃まで１〜３時間で昇温し、その温度で３
０分間保持して熱処理を行い、同気流中で常温まで冷却
し、組成割合が２０％Ｆｅ−１２％Ｍｎ２０３−４％Ｒ
ｕからなる本発明方法による三元組成系触媒２８部を得
た。この触媒上へ第１表に示す組成よりなる低カロリー
の供試ガスを第３表に示す条件で通過させたところ、第
３表に示す組成よりなる高カロリーのガスを得た。Next, the temperature of the ternary composition catalyst was raised from room temperature to 700°C over 1 to 3 hours in a 10.094 hydrogen stream, and at that temperature
Heat treatment was performed by holding for 0 minutes, cooling to room temperature in the same air flow, and the composition ratio was 20%Fe-12%Mn203-4%R.
28 parts of a ternary composition catalyst according to the method of the present invention consisting of u was obtained. When a low calorie test gas having the composition shown in Table 1 was passed over this catalyst under the conditions shown in Table 3, a high calorie gas having the composition shown in Table 3 was obtained.
実施例３〜６
アルミナ担体を実施例１と同様にして第２表に示す薬品
で処理して同表に示す触媒を得た。これらの触媒に第１
表に示す組成の低カロリーガスを第３表に示す条件で通
過させ同表下欄に示す組成の炭化水素含有ガスを得た。Examples 3 to 6 An alumina carrier was treated with the chemicals shown in Table 2 in the same manner as in Example 1 to obtain the catalysts shown in Table 2. These catalysts have the first
A low calorie gas having the composition shown in the table was passed under the conditions shown in Table 3 to obtain a hydrocarbon-containing gas having the composition shown in the lower column of the table.
尚第２表および第３表には実施例１および実施例２の結
果も共に併記する。The results of Examples 1 and 2 are also listed in Tables 2 and 3.
本発明は概略以上の様に構成されており、水素および一
酸化炭素を含むガス、あるいは更に二酸化炭素を含む低
カロリーガス、例えばコークス炉ガスを本発明の触媒に
接触させると、炭素数１〜４特に２〜４の炭化水素をよ
り多く含みＳＮＧとして好適な高カロリーガスを得るこ
とができ、しかも耐熱性にすぐれた寿命の長い触媒であ
る。The present invention is roughly configured as described above, and when a gas containing hydrogen and carbon monoxide, or a low-calorie gas further containing carbon dioxide, such as coke oven gas, is brought into contact with the catalyst of the present invention, In particular, it is a catalyst that contains a large amount of 2 to 4 hydrocarbons, can obtain a high-calorie gas suitable for SNG, and has excellent heat resistance and a long life.
Claims (1)
化マンガンと白金族金属とを組み合わせてシリカおよび
／またはアルミナよりなる担体に担持させてなり、前記
鉄および／またはコバルトの配合量を、担体を含む全触
媒重量に対して１５％を超え２５％以下としてなること
を特徴とする還元触媒。(1) A combination of iron and/or cobalt as a catalyst substrate, manganese oxide and platinum group metal is supported on a carrier made of silica and/or alumina, and the amount of iron and/or cobalt is adjusted to A reducing catalyst characterized in that it accounts for more than 15% and less than 25% of the total weight of the catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62147320A JPS6323742A (en) | 1987-06-13 | 1987-06-13 | Reduction catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62147320A JPS6323742A (en) | 1987-06-13 | 1987-06-13 | Reduction catalyst |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58023619A Division JPS59147641A (en) | 1983-02-15 | 1983-02-15 | Preparation of catalyst for manufacturing high-calorie gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6323742A true JPS6323742A (en) | 1988-02-01 |
| JPH0558776B2 JPH0558776B2 (en) | 1993-08-27 |
Family
ID=15427518
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62147320A Granted JPS6323742A (en) | 1987-06-13 | 1987-06-13 | Reduction catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6323742A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5102851A (en) * | 1988-12-28 | 1992-04-07 | Den Norske Stats Oljeselskap A.S. | Supported catalyst for hydrocarbon synthesis |
| JP2010149109A (en) * | 2008-11-18 | 2010-07-08 | Osaka Gas Co Ltd | Catalyst for producing high calorie gas, production method therefor, and method for producing high calorie gas using catalyst for producing high calorie gas |
-
1987
- 1987-06-13 JP JP62147320A patent/JPS6323742A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5102851A (en) * | 1988-12-28 | 1992-04-07 | Den Norske Stats Oljeselskap A.S. | Supported catalyst for hydrocarbon synthesis |
| JP2010149109A (en) * | 2008-11-18 | 2010-07-08 | Osaka Gas Co Ltd | Catalyst for producing high calorie gas, production method therefor, and method for producing high calorie gas using catalyst for producing high calorie gas |
| JP2014073492A (en) * | 2008-11-18 | 2014-04-24 | Osaka Gas Co Ltd | Catalyst for producing high-calorie gas, method for producing the catalyst, and method for producing high-calorie gas using catalyst for producing high-calorie gas |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0558776B2 (en) | 1993-08-27 |
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