JPH03118834A - Catalyst for production of 3c hydrocarbon and production of 3c hydrocarbon - Google Patents
Catalyst for production of 3c hydrocarbon and production of 3c hydrocarbonInfo
- Publication number
- JPH03118834A JPH03118834A JP1258137A JP25813789A JPH03118834A JP H03118834 A JPH03118834 A JP H03118834A JP 1258137 A JP1258137 A JP 1258137A JP 25813789 A JP25813789 A JP 25813789A JP H03118834 A JPH03118834 A JP H03118834A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- hydrocarbons
- oxide
- methane
- crystal structure
- 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 58
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 43
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 239000004215 Carbon black (E152) Substances 0.000 title abstract 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000013078 crystal Substances 0.000 claims abstract description 20
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000010436 fluorite Substances 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 15
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 abstract description 14
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 9
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 9
- 239000001294 propane Substances 0.000 abstract description 7
- 229910052790 beryllium Inorganic materials 0.000 abstract description 2
- 229910052791 calcium Inorganic materials 0.000 abstract description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract description 2
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052749 magnesium Inorganic materials 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract 2
- 239000002253 acid Substances 0.000 abstract 1
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 19
- 238000000034 method Methods 0.000 description 7
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 6
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- -1 olefin hydrocarbons Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical class [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052730 francium Inorganic materials 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229910052725 zinc 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
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、メタン含有ガスおよび酸素含有ガスを用いて
プロパンやプロピレン等のＣ５炭化水素を製造する方法
、及び該製造方法に用いる触媒に関するものである。Detailed Description of the Invention [Industrial Application Field] The present invention relates to a method for producing C5 hydrocarbons such as propane and propylene using a methane-containing gas and an oxygen-containing gas, and a catalyst used in the production method. It is.
［従来の技術］
エチレンやプロピレン等の低級オレフィン系炭化水素は
、炭素−炭素に２重粘合を有し反応性に富む物質であり
、有機化学工業における最も重要な基礎物質として大量
に生産されている。[Prior art] Lower olefinic hydrocarbons such as ethylene and propylene are highly reactive substances with carbon-carbon double viscosity, and are produced in large quantities as the most important basic materials in the organic chemical industry. ing.
低級オレフィン系炭化水素の製造に当たフては、従来■
エタン、プロパン、ブタン等を主成分とする湿性天然ガ
スを原料として製造する方法、■ナフサを原料とし、こ
わを熱分解する方法等が主流を占めていた。しかしなが
ら「石油ショックｊ以来、低級オレフィン系炭化水素製
造用原料の多様化が図られる様になり、豊富な地下資源
である乾性天然ガスが注目される様になり、乾性天然ガ
スの主成分であるメタンから低級オレフィン系炭化水素
を製造する技術が開発されつつある。In the production of lower olefin hydrocarbons, conventional methods ■
The mainstream methods were manufacturing methods using wet natural gas containing ethane, propane, butane, etc. as a raw material, and (2) using naphtha as a raw material and thermally decomposing the stiffness. However, since the oil crisis, raw materials for producing lower olefin hydrocarbons have been diversified, and dry natural gas, which is an abundant underground resource, has attracted attention, and Techniques for producing lower olefin hydrocarbons from methane are being developed.
例えばＧ、に、Ｋｅｌｌｅｒらは、「ジャーナル・オブ
・カタリシス」 （第７３巻、 １９８２年）において
、メタン含有ガスと酸素含有ガスを触媒の存在のもとで
接触させ、エチレンやエタン等を製造する技術を提案し
ている。そして用いる触媒としては、マンガンやカドミ
ウムの酸化物をアルミナに担持させた触媒が有効である
ことを示している。For example, in "Journal of Catalysis" (Vol. 73, 1982), G. Keller et al. reported that methane-containing gas and oxygen-containing gas were brought into contact in the presence of a catalyst to produce ethylene, ethane, etc. We are proposing a technology to do this. As for the catalyst used, it has been shown that a catalyst in which manganese or cadmium oxides are supported on alumina is effective.
一方特開昭６１−２０７３４６号には、酸化鉛、または
酸化鉛と酸化マンガンを触媒として用い、メタンからエ
チレンやエタンを製造する技術が示されている。On the other hand, JP-A-61-207346 discloses a technique for producing ethylene and ethane from methane using lead oxide or lead oxide and manganese oxide as a catalyst.
［発明が解決しようとする課題］
上記各技術は、メタンの酸化カップリングによって低級
炭化水素を得るものであるが、いずれもエタンやエチレ
ン等の０２炭化水素を製造の主目的とする為のものであ
る。[Problem to be solved by the invention] Each of the above-mentioned technologies obtains lower hydrocarbons by oxidative coupling of methane, but all of them are aimed at producing 02 hydrocarbons such as ethane and ethylene as the main purpose. It is.
これに対しプロパンやプロピレン等の０３炭化水素をメ
タンの酸化カップリングによって製造するという技術は
これまで報告されておらず、この様なＣ３炭化水素が高
効率で得られる技術の開発が望まれている。特にプロピ
レンは、イソプロピルアルコール、アセトン、プロピレ
ンオキシド等の製造用出発物質として有用であり、この
様なプロピレンを酸化カップリング法によって好収率に
得る方法の開発が強く望まれている。On the other hand, no technology has been reported to date to produce 03 hydrocarbons such as propane and propylene by oxidative coupling of methane, and the development of a technology that can produce such C3 hydrocarbons with high efficiency is desired. There is. In particular, propylene is useful as a starting material for the production of isopropyl alcohol, acetone, propylene oxide, etc., and there is a strong desire to develop a method for obtaining such propylene in good yield by oxidative coupling.
本発明はこうした技術的課題を解決する為になされたも
のであって、プロパンやプロピレン等のＣ５炭化水素を
メタンの酸化カップリングによって製造する為の技術を
提供するものであり、特にＣ８炭化水素製造に最適な触
媒および該触媒を用いてＣ３炭化水素を効率良く製造す
る方法を実現するものである。The present invention was made to solve these technical problems, and provides a technology for producing C5 hydrocarbons such as propane and propylene by oxidative coupling of methane. The present invention aims to realize a catalyst optimal for production and a method for efficiently producing C3 hydrocarbons using the catalyst.
［課題を解決する為の手段］
本発明に係る触媒は、蛍石型結晶構造を有する酸化物に
ＩＩ Ａ族元素が固溶化された複合酸化物を主成分とす
る点に要旨を有するものである。また上記触媒中にアル
カリ金属を含有させることも有効であり、こうした触媒
構成を採用することによって、本発明の効果がより一層
達成される。尚蛍石型結晶構造を有する酸化物に対し、
ＩＩ Ａ族以外の２価をとり得る元素及びＩＩＩ族元素
よりなる群から選ばれる元素を上記触媒中に含有させる
ことも有効であり、この場合はアルカリ金属を必ず含有
させる必要がある。[Means for Solving the Problems] The main feature of the catalyst of the present invention is that the main component is a composite oxide in which a Group II A element is dissolved in an oxide having a fluorite crystal structure. be. It is also effective to include an alkali metal in the catalyst, and by adopting such a catalyst configuration, the effects of the present invention can be further achieved. Furthermore, for oxides with a fluorite crystal structure,
It is also effective to include in the above catalyst an element selected from the group consisting of divalent elements other than group IIA elements and group III elements, and in this case, it is necessary to necessarily include an alkali metal.
上記触媒を用いて、Ｃ３炭化水素を製造するに当たフて
は、通常の「メタンの酸化カップリング法」に従えばよ
く、上記触媒の存在下でメタン含有ガスおよび酸素含有
ガスを接触させればよいが、その反応温度は５００〜７
００℃と比較的低温とするのが好ましく、こうした触媒
および温度条件下によってＣ５炭化水素が効率よく製造
される。To produce C3 hydrocarbons using the above catalyst, it is sufficient to follow the usual "methane oxidative coupling method", in which methane-containing gas and oxygen-containing gas are brought into contact in the presence of the above catalyst. However, the reaction temperature is 500-7
A relatively low temperature of 00° C. is preferable, and C5 hydrocarbons can be efficiently produced under such catalyst and temperature conditions.
［作用］
本発明者らは、メタンの酸化カップリングによってプロ
パンやプロピレン等のＣ５炭化水素を得るという観点か
ら、使用する触媒や温度条件等について様々な検討を加
えた。その結果、まず反応温度を比較的低温側に制御す
れば、Ｃ５炭化水素が生成し易くなるとの知見が得られ
た。即ち、これまでの酸化カップリング法では、７５０
℃以上の比較的高い温度条件下によって反応を行なうの
が常識化されており、低温側での実施はなされていなか
ったのであるが、本発明者らが実験によって確認したと
ころによると、５００〜７００℃の比較的低温側の温度
条件下でメタンの酸化カップリングを行なえば、これま
での常識を覆えしてＣ３炭化水素が相当の選択率をもっ
て生成する様になるということが分かった。またこのと
き用いる触媒として、下記■〜■の触媒が最適であるこ
とを見出し、本発明を完成した。[Function] From the viewpoint of obtaining C5 hydrocarbons such as propane and propylene by oxidative coupling of methane, the present inventors have made various studies regarding the catalyst to be used, temperature conditions, etc. As a result, it was found that C5 hydrocarbons can be easily produced by first controlling the reaction temperature to a relatively low temperature side. That is, in the conventional oxidative coupling method, 750
It is common knowledge that the reaction should be carried out under relatively high temperature conditions of 500°C or above, and it has not been carried out at low temperatures. It has been found that if oxidative coupling of methane is carried out under relatively low temperature conditions of 700°C, C3 hydrocarbons can be produced with considerable selectivity, contrary to conventional wisdom. Furthermore, the inventors have found that the following catalysts (1) to (4) are most suitable as catalysts to be used at this time, and have completed the present invention.
■：蛍石型結晶構造を有する酸化物にＩＩ Ａ族元素が
固溶化された複合酸化物を主成分とする触媒。(2): A catalyst whose main component is a composite oxide in which a Group II A element is dissolved in an oxide having a fluorite crystal structure.
■：■の触媒にアルカリ金属を含有させた複合酸化物を
主成分とする触媒。■: A catalyst whose main component is a composite oxide containing an alkali metal in the catalyst of ■.
■：蛍石型結晶構造を有する酸化物に、ＩＩ Ａ族に属
さない２価または３価を取り得る元素の１種または２種
以上及びアルカリ金属が固溶化された複合酸化物を主成
分とする触媒。■: The main component is a composite oxide in which one or more divalent or trivalent elements that do not belong to Group II A and an alkali metal are dissolved in an oxide having a fluorite crystal structure. catalyst.
上記■の触媒がＣ５炭化水素製造に最適である理由につ
いては全てを解明し得た訳ではないが、おそらく蛍石型
結晶構造を有する酸化物にＩＩ Ａ族元素が固溶化され
た複合酸化物は、酸素欠陥をもつ安定した結晶構造をと
り、この構造の触媒がメタンの酸化カップリングに際し
てメタンを３分子集合させＣ５炭化水素製造を生成し得
る様になフたものと考えられる。Although we have not yet fully elucidated the reason why the catalyst described in (1) above is optimal for producing C5 hydrocarbons, it is probably a composite oxide in which Group II A elements are dissolved in an oxide with a fluorite crystal structure. It is thought that the catalyst has a stable crystal structure with oxygen vacancies, and that the catalyst with this structure is able to assemble three molecules of methane during oxidative coupling of methane to produce C5 hydrocarbons.
また本発明者らの実験によると、本発明に係る触媒は塩
基性であることが必要であり、ＩＩ Ａ族元素を含有し
た触媒は元来塩基性を示すことから、上記■の触媒では
ＩＩ Ａ族の元素（Ｂｅ、Ｍｇ。Furthermore, according to experiments conducted by the present inventors, the catalyst according to the present invention needs to be basic, and catalysts containing Group II A elements are inherently basic. Group A elements (Be, Mg.
Ｃａ、Ｓｒ、Ｂａ、Ｒａ）は上記結晶構造を有すると共
に、塩基性を示す。従って塩基性を高めるという観点か
ら、上記の触媒に対してＬｉ。Ca, Sr, Ba, Ra) have the above crystal structure and exhibit basicity. Therefore, from the viewpoint of increasing basicity, Li is added to the above catalyst.
Ｎａ、に、Ｒｈ、Ｃｓ、Ｆｒ等のアルカリ金属を含有さ
せることも有効であり（上記触媒■）、これによってＣ
１収率を更に高めることができる。It is also effective to incorporate alkali metals such as Rh, Cs, and Fr into Na (catalyst ① above);
1 yield can be further increased.
尚酸素欠陥をもつ安定した結晶構造は、蛍石型結晶構造
を有する酸化物に対しＨＡ族に属さない２価を取り得る
元素例えばＩＩ Ｂ族（Ｚｎ、Ｃｄ等）、または３価を
取り得る元素例えばＩＩＩ Ｂ族（Ｇａ、Ｉｎ、ＴＩ等
）等を固溶化することによっても得られるが、この場合
は複合酸化物が塩基性を示さないので、アルカリ金属を
含有させて塩基性にする必要がある（上記触媒■）。ち
なみに本発明者らが実験によって確認したところによる
と、Ｃａ０−ＺｒＯ，複合酸化物は正方晶型であったが
、これを触媒として用いてもＣ５炭化水素は生成しなか
った。In addition, a stable crystal structure with oxygen defects is an element that does not belong to the HA group and can be divalent, such as II B group (Zn, Cd, etc.), or can be trivalent, for an oxide having a fluorite crystal structure. It can also be obtained by making a solid solution of elements such as group III B (Ga, In, TI, etc.), but in this case, since the composite oxide does not show basicity, it is necessary to contain an alkali metal to make it basic. (catalyst ■ above). Incidentally, the present inventors confirmed through experiments that the Ca0-ZrO composite oxide was a tetragonal crystal type, but no C5 hydrocarbons were produced even when this was used as a catalyst.
尚本発明で用いる「蛍石型結晶構造を有する酸化物」と
しては、ＺｒＯ２が代表例として挙げられるが、その他
ＨｆＯ２、ＣｅＯ２、Ｐｒ０２ 。A representative example of the "oxide having a fluorite crystal structure" used in the present invention is ZrO2, but other examples include HfO2, CeO2, and Pr02.
ＴｂＯ，等がある。There are TbO, etc.
本発明においては、５００〜７００℃の温度範囲でメタ
ンを酸化カップリングすることによってＣ３炭化水素が
得られるのは上述した通りであるが、これは温度条件が
５ｏｏ℃未満ではメタンの酸化（社務）反応が進行せず
、また７００ｔを超えるとエタンやエチレン等の０２炭
化水素が生成してくるからである。As mentioned above, in the present invention, C3 hydrocarbons are obtained by oxidative coupling of methane in the temperature range of 500 to 700°C. ) This is because the reaction does not proceed and if the amount exceeds 700 tons, 02 hydrocarbons such as ethane and ethylene are produced.
以下本発明を実施例によって更に詳細に説明するが、下
記実施例は本発明を限定する性質のものではなく、前・
後期の趣旨に徴して設計変更することはいずれも本発明
の技術的範囲に含まれるものである。Hereinafter, the present invention will be explained in more detail with reference to examples, but the following examples are not intended to limit the present invention.
Any design changes that reflect the purpose of the latter part are included within the technical scope of the present invention.
［実施例］
実施例１
日本触媒化学工業製のジルコニアゾルに硝酸カルシウム
を様々な割合で加えて加熱攪拌した後乾燥し、４００℃
で２時間焼成した夜更にａＯＯ℃で４時間焼成し、４．
８，２０ｍｏ１％Ｃａ０−ＺｒＯ，触媒を製造した。尚
得られた触媒は、ＸＲＤ測定によると正方晶型か立法晶
型のいずれかを示していた。[Example] Example 1 Calcium nitrate was added in various proportions to zirconia sol manufactured by Nippon Shokubai Chemical Industry Co., Ltd., heated and stirred, and then dried at 400°C.
4. After baking for 2 hours at 4.
A catalyst containing 8.20 mo1% Ca0-ZrO was produced. According to XRD measurement, the obtained catalyst exhibited either a tetragonal crystal type or a cubic crystal type.
次に上記触媒を用い、様々な温度条件下でメタンの酸化
カップリングを行ない、Ｃ３炭化水素の生成状況を調査
した。このとき上記触媒は０．０５ｇ用い、ＣＨ４：０
２ ：Ｈｅの混合ガスを流速５０ｍ１／分の割合で流
した。その結果は、第１表および第２表に示す通りであ
り、５００〜７ｏｏ℃の温度範囲で０３炭化水素が得ら
れていた。Next, using the above catalyst, oxidative coupling of methane was carried out under various temperature conditions, and the production status of C3 hydrocarbons was investigated. At this time, 0.05 g of the above catalyst was used, and CH4:0
2: A mixed gas of He was flowed at a flow rate of 50 ml/min. The results are shown in Tables 1 and 2, and 03 hydrocarbons were obtained in the temperature range of 500 to 70°C.
実施例２
硝酸カルシウムの代わりに硝酸マグルシウムを用いる以
外は実施例１と同様として８ｍｏ１％ＭｇＯ−ＺｒＯ２
触媒を調製し、この触媒を用いて実施例１と同様にして
メタンの酸化カップリングを行ない、Ｃ３炭化水素の生
成状況を調査した。その結果は、第３表に示す通りであ
り、低温側でＣ５炭化水素の生成が肥められた。Example 2 Same as Example 1 except that maglucium nitrate was used instead of calcium nitrate, but 8 mo1% MgO-ZrO2
A catalyst was prepared, and using this catalyst, oxidative coupling of methane was carried out in the same manner as in Example 1, and the production status of C3 hydrocarbons was investigated. The results are shown in Table 3, and the production of C5 hydrocarbons was enhanced on the low temperature side.
実施例３
日本触媒化学工業製のジルコニアゾルに硝酸カルシウム
および硝酸リチウムを加えて加熱攪拌した後乾燥し、４
００℃で２時間焼成した夜更にａＯＯ℃で４時間焼成し
、５ｍｏ１％Ｌｉ−８ｍｏ１％Ｃａ０−ＺｒＯｚ触媒を
製造した。得られた触媒は、ＸＲＤ測定によると正方晶
型を示していた。Example 3 Calcium nitrate and lithium nitrate were added to zirconia sol manufactured by Nippon Shokubai Chemical Industry Co., Ltd., heated and stirred, and then dried.
At night after firing at 00°C for 2 hours, the mixture was further fired at aOO°C for 4 hours to produce a 5mol%Li-8mo1%Ca0-ZrOz catalyst. The obtained catalyst exhibited a tetragonal crystal type according to XRD measurement.
次に上記触媒を用い、様々な温度条件下でメタンの酸化
カップリングを行ない、Ｃ５炭化水素の生成状況を調査
した。尚このときの酸化カップリング条件は実施例１と
同様である。その結果は第４表に示す通りであり、５０
０〜７００℃の温度範囲でＣ５炭化水素が得られていた
。Next, using the above catalyst, oxidative coupling of methane was carried out under various temperature conditions, and the production status of C5 hydrocarbons was investigated. The oxidative coupling conditions at this time are the same as in Example 1. The results are shown in Table 4, and 50
C5 hydrocarbons were obtained in the temperature range from 0 to 700°C.
実施例４
硝酸カルシウムの代わりに硝酸マグルシウムまたは硝酸
カドニウムを用いる以外は、実施例３と同様にして５ｍ
ｏ１％ＬＬ−ａｎｏ１％ＭｇＯ−ＺｒＯ２触媒と５ｍｏ
１％Ｌｉ−８ｍｏ１％Ｃａｄ−ＺｒＯ２触媒を調製し、
これらの触媒を用いて実施例１〜３と同様にしてメタン
の酸化カップリングを行ない、Ｃ５炭化水素の生成状況
を調査した。その結果は、第５表に示す通りであり、低
温側で０３炭化水素の生成が認められた。Example 4 A 5 m
o1%LL-ano1%MgO-ZrO2 catalyst and 5mo
Prepare 1% Li-8mo1%Cad-ZrO2 catalyst,
Oxidative coupling of methane was carried out using these catalysts in the same manner as in Examples 1 to 3, and the production status of C5 hydrocarbons was investigated. The results are shown in Table 5, and the formation of 03 hydrocarbons was observed on the low temperature side.
実施例５
日本触媒化学工業製のジルコニアゾルに硝酸イツトリウ
ムを加えると共に、各種割合の硝酸リチウムを加えて加
熱攪拌した後乾燥し、４００℃で２時間焼成した夜更に
８００℃で４時間焼成し、Ｌｉを様々な割合で含有させ
た４ ｍｏ１％’（２０２−ＺｒＯ２触媒を製造した。Example 5 Yttrium nitrate was added to zirconia sol manufactured by Nippon Shokubai Chemical Industry Co., Ltd., as well as lithium nitrate in various proportions, heated and stirred, dried, fired at 400°C for 2 hours, and further fired at 800°C for 4 hours at night. 4 mol%' (202-ZrO2 catalysts) containing Li in various proportions were prepared.
尚得られた触媒は、ＸＲＤ測定によると正方晶型を示し
ていた。The obtained catalyst had a tetragonal crystal structure according to XRD measurement.
次に上記各触媒を用い、高温側と低温後の温度条件下で
メタンの酸化カップリングを行ない、Ｃ５炭化水素の生
成状況を調査した。尚酸化カップリング条件は実施例１
〜４と同様である。その結果は第６表に示す通りであり
、低温側で０３炭化水素の生成が認められた。Next, using each of the above catalysts, oxidative coupling of methane was performed under high temperature and low temperature conditions, and the production status of C5 hydrocarbons was investigated. The oxidative coupling conditions are as in Example 1.
- Same as 4. The results are shown in Table 6, and the formation of 03 hydrocarbons was observed on the low temperature side.
実施例６
硝酸イツトリウムの代わりにＬａ、Ｉｎ、ＴＩの各硝酸
塩を用いる以外は、実施例５と同様にして５ ｍｏ１％
；Ｌｉ −４ｍｏ１４Ｌａ２０ｓ −Ｚｒ０ｚ触媒、５
ｍｏｌＸｌ、ｉ−４ｍｏｌ零Ｉｎ２Ｏ５−ＺｒＯ２触媒
、および５ｍｏｌｋＬｉ４ｍｏｌ零ＴＩＪ３− ＺｒＯ
２触媒を調製し、これらの触媒を用いて実施例５と同様
にしてメタンの酸化カップリングを行ない、Ｃ３炭化水
素の生成状況を調査した。その結果は第７表に示す通り
であり、低温側でＣ５炭化水素の生成が認められた。Example 6 5 mo1% was prepared in the same manner as in Example 5 except that La, In, and TI nitrates were used instead of yttrium nitrate.
;Li-4mo14La20s-Zr0z catalyst, 5
molXl, i-4mol zero In2O5-ZrO2 catalyst, and 5molkLi4mol zeroTIJ3-ZrO
Two catalysts were prepared, and using these catalysts, oxidative coupling of methane was carried out in the same manner as in Example 5, and the production status of C3 hydrocarbons was investigated. The results are shown in Table 7, and the formation of C5 hydrocarbons was observed on the low temperature side.
［発明の効果］
以上述べた如く本発明によれば、プロパンやプロピレン
等のＣ５炭化水素をメタンの酸化カップリングによって
効率よく製造することができる様になった。[Effects of the Invention] As described above, according to the present invention, C5 hydrocarbons such as propane and propylene can be efficiently produced by oxidative coupling of methane.
手続補正書 （自発） 平成元年１０月 ６日Procedural amendment (spontaneous) October 1989 6th day
Claims (4)
溶化された複合酸化物を主成分とすることを特徴とする
Ｃ＿３炭化水素製造用触媒。(1) A catalyst for producing C_3 hydrocarbons, characterized in that the main component is a composite oxide in which a Group IIA element is dissolved in an oxide having a fluorite crystal structure.
アルカリ金属元素が固溶化された複合酸化物を主成分と
することを特徴とするＣ＿３炭化水素製造用触媒。(2) A catalyst for producing C_3 hydrocarbons, characterized in that the main component is a composite oxide in which a group IIA element and an alkali metal element are dissolved in an oxide having a fluorite crystal structure.
ない２価を取り得る元素及びIII族元素よりなる群から
選ばれる１種または２種以上の元素並びにアルカリ金属
元素が固溶化された複合酸化物を主成分とすることを特
徴とするＣ＿３炭化水素製造用触媒。(3) One or more elements selected from the group consisting of divalent elements that do not belong to Group IIA and Group III elements and an alkali metal element are dissolved in an oxide having a fluorite crystal structure. A catalyst for producing C_3 hydrocarbons, characterized in that the main component is a composite oxide produced by
５００〜７００℃の範囲で、請求項（１）〜（３）のい
ずれかの触媒に接触させてＣ＿３炭化水素を得ることを
特徴とするＣ＿３炭化水素の製造方法。(4) C_3 hydrocarbons are obtained by contacting a methane-containing gas and an oxygen-containing gas with the catalyst according to any one of claims (1) to (3) at a reaction temperature of 500 to 700°C. Method for producing C_3 hydrocarbons.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1258137A JPH03118834A (en) | 1989-10-02 | 1989-10-02 | Catalyst for production of 3c hydrocarbon and production of 3c hydrocarbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1258137A JPH03118834A (en) | 1989-10-02 | 1989-10-02 | Catalyst for production of 3c hydrocarbon and production of 3c hydrocarbon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03118834A true JPH03118834A (en) | 1991-05-21 |
Family
ID=17316032
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1258137A Pending JPH03118834A (en) | 1989-10-02 | 1989-10-02 | Catalyst for production of 3c hydrocarbon and production of 3c hydrocarbon |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03118834A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007209977A (en) * | 2006-01-20 | 2007-08-23 | Petrochina Co Ltd | Heterogeneous solid base catalyst, and production process and use thereof |
-
1989
- 1989-10-02 JP JP1258137A patent/JPH03118834A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007209977A (en) * | 2006-01-20 | 2007-08-23 | Petrochina Co Ltd | Heterogeneous solid base catalyst, and production process and use thereof |
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