JP5303971B2 - Methanol synthesis method - Google Patents
Methanol synthesis method Download PDFInfo
- Publication number
- JP5303971B2 JP5303971B2 JP2008063249A JP2008063249A JP5303971B2 JP 5303971 B2 JP5303971 B2 JP 5303971B2 JP 2008063249 A JP2008063249 A JP 2008063249A JP 2008063249 A JP2008063249 A JP 2008063249A JP 5303971 B2 JP5303971 B2 JP 5303971B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- gas
- reaction
- methanol
- carbon dioxide
- 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 - Fee Related
Links
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
本発明は、二酸化炭素（ＣＯ２）および水素（Ｈ２）からメタノールを合成するメタノール合成方法に関する。 The present invention relates to a methanol synthesis method for synthesizing methanol from carbon dioxide (CO 2 ) and hydrogen (H 2 ).
メタノールは主要化学品の一つであり、古くからメタノール合成触媒の開発研究が行われており、酸化銅−酸化亜鉛を含む三元または四元系触媒が、一酸化炭素と水素の混合ガス（合成ガス）からのメタノール合成において高い活性を有していることが知られている（特許文献１〜３等参照）。 Methanol is one of the main chemicals, and research and development of methanol synthesis catalysts has been conducted for a long time, and ternary or quaternary catalysts containing copper oxide-zinc oxide are mixed with carbon monoxide and hydrogen gas ( It is known to have high activity in methanol synthesis from synthesis gas) (see Patent Documents 1 to 3, etc.).
メタノールは、メチルターシャリーブチルエーテル（ＭＴＢＥ）、石油化学中間製品などの原料として、また燃料としての需要も増えることが期待されている。 Methanol is expected to increase demand as a raw material for fuel such as methyl tertiary butyl ether (MTBE) and petrochemical intermediate products, and as a fuel.
一方、発電所、工場、自動車等の人間の社会的活動に伴って大気中に排出される二酸化炭素は地球温暖化の主たる原因であることが知られており、近年、この二酸化炭素の排出量を削減することが地球環境の保護の大きな課題となっている。そのため、発電所等の排煙や大気中の二酸化炭素を固定化し除去する方法が種々検討されている。
On the other hand, carbon dioxide released into the atmosphere in response to human social activities such as power plants, factories, and automobiles is known to be the main cause of global warming. Reducing environmental issues is a major issue for protecting the global environment . Therefore, various methods for fixing and removing flue gas from power plants and the like and carbon dioxide in the atmosphere have been studied.
しかしながら、二酸化炭素と水素からのメタノール合成法に関しては報告例も少なく、生物的あるいは物理的に二酸化炭素を固定化する方法に比べると、エネルギーの低減が図れる可能性があるが、基礎研究の段階である。 However, there are few reports on the synthesis of methanol from carbon dioxide and hydrogen, and there is a possibility that energy can be reduced compared with the method of biologically or physically immobilizing carbon dioxide. It is.
例えば、特許文献４には、担体として酸化ランタン等の金属酸化物を使用し、銅と酸化亜鉛を担体に担持した触媒を用いて、二酸化炭素と水素からメタノールを合成する方法が提案されているが、ランタン含有量が多いと却ってメタノール生成量が少なくなる傾向にある（本願明細書の実施例１参照）。 For example, Patent Document 4 proposes a method of synthesizing methanol from carbon dioxide and hydrogen using a metal oxide such as lanthanum oxide as a support and using a catalyst in which copper and zinc oxide are supported on the support. However, when the lanthanum content is high, the amount of methanol produced tends to decrease (see Example 1 of the present specification).
特許文献５には、銅、亜鉛、アルミニウムおよびガリウムの各酸化物と、アルカリ土類金属元素およびランタンの金属酸化物の一種以上とを含有するメタノール合成触媒を用いて、二酸化炭素と水素の混合ガスからメタノールを合成する方法が提案されている。このメタノール合成触媒は従来触媒に比べてメタノール合成活性が高いと報告されているが、反応温度（実施例５によれば２１０℃）などの点で解決すべき課題もある。 Patent Document 5 discloses a mixture of carbon dioxide and hydrogen using a methanol synthesis catalyst containing each of oxides of copper, zinc, aluminum and gallium and one or more of alkaline earth metal elements and lanthanum metal oxides. A method for synthesizing methanol from gas has been proposed. This methanol synthesis catalyst is reported to have higher methanol synthesis activity than the conventional catalyst, but there are also problems to be solved in terms of the reaction temperature (210 ° C. according to Example 5).
さらに特許文献６には、二酸化炭素と水素の混合物に、触媒存在下でマイクロ波を照射することにより、メタノールが合成されることが報告されているが、メタノール転化率のなどの点において課題を有している。
触媒化学的な方法は反応速度が遅く、気相還元法を用いれば火力発電所の煙道等から排出される大量の二酸化炭素を短時間で処理可能とも考えられているが、メタノール等の液状炭化水素に直接転化するためには、高圧下での反応が必要であるため、短時間での処理が難しい。二酸化炭素と水素を用いて気相還元する方法としては、常圧下で反応が進行する反応として、下記の反応が知られている。
ＣＯ２ ＋ Ｈ２ → ＣＯ＋ Ｈ２Ｏ
The catalytic chemical method has a slow reaction rate, and it is considered that a large amount of carbon dioxide discharged from the flue of a thermal power plant can be processed in a short time by using a gas phase reduction method. In order to directly convert to hydrocarbon, a reaction under high pressure is required, so that it is difficult to process in a short time. As a method for vapor phase reduction using carbon dioxide and hydrogen, the following reaction is known as a reaction that proceeds under normal pressure.
CO 2 + H 2 → CO + H 2 O
この反応は吸熱反応であるため、一般には高温になればなるほど平衡が右側にシフトして、二酸化炭素が一酸化炭素に転化する比率（転化率）は増加するが、高温を維持するにはエネルギーを投入する必要があり、このエネルギー源として化石燃料を使用すれば二酸化炭素の排出量を低減したことにはならなくなる。 Since this reaction is an endothermic reaction, in general, the higher the temperature, the more the equilibrium shifts to the right, and the rate at which carbon dioxide is converted to carbon monoxide (conversion) increases. If fossil fuel is used as this energy source, the amount of carbon dioxide emissions will not be reduced.
従って、できるだけ低エネルギーで、化学平衡状態の転化率に近い転化特性を得られるか否かが、二酸化炭素からのメタノール合成における重要な課題である。 Therefore, whether or not conversion characteristics close to the conversion rate in a chemical equilibrium state can be obtained with as low energy as possible is an important issue in the synthesis of methanol from carbon dioxide.
本発明は、上記事情に鑑み、低エネルギー（すなわち、低温）で二酸化炭素と水素からメタノールを合成することが可能な、メタノール合成法を提供することを課題とする。 In view of the above circumstances, an object of the present invention is to provide a methanol synthesis method capable of synthesizing methanol from carbon dioxide and hydrogen with low energy (that is, low temperature).
前記課題を解決するため、本発明者らは鋭意検討した。そして、従来のＣｕＯ−ＺｎＯ系触媒に付加する金属元素としてランタンに着目し、ランタン含有量を種々検討した結果最適含有量が存在すること、さらに、触媒反応をマイクロ波による加熱状態で行わせることによりより少ないエネルギーで合成できること、を見出し、本発明に到達した。 In order to solve the above problems, the present inventors have intensively studied. Then, paying attention to lanthanum as a metal element to be added to the conventional CuO-ZnO-based catalyst, there is an optimum content as a result of various investigations on the lanthanum content, and further, the catalytic reaction is performed in a heated state by microwaves. And the present invention was reached.
すなわち、本発明は以下の通りである。
（１）マイクロ波を照射し、触媒存在下に二酸化炭素と水素を反応させてメタノールを合成する方法であって、前記触媒が銅酸化物、亜鉛酸化物およびランタン酸化物からなり、該ランタンの量が全触媒金属を基準として金属として０．５〜１０質量％であることを特徴とするメタノール合成方法。
（２）前記触媒における銅元素と亜鉛元素の比率が、９８：２〜３０：７０である前記（１）に記載のメタノール合成方法。
（３）前記触媒を充填した触媒充填層に、二酸化炭素と水素からなるガスを導入し、該触媒充填層にマイクロ波を照射して反応させる前記（１）または（２）に記載のメタノール合成方法。
That is, the present invention is as follows.
(1) A method of synthesizing methanol by irradiating microwaves and reacting carbon dioxide and hydrogen in the presence of a catalyst, wherein the catalyst comprises copper oxide, zinc oxide and lanthanum oxide, A methanol synthesis method characterized in that the amount is 0.5 to 10% by mass as a metal based on the total catalytic metal.
(2) The methanol synthesis method according to (1), wherein the ratio of the copper element and the zinc element in the catalyst is 98: 2 to 30:70.
(3) Methanol synthesis according to (1) or (2), wherein a gas comprising carbon dioxide and hydrogen is introduced into the catalyst packed bed filled with the catalyst, and the catalyst packed bed is irradiated with microwaves for reaction. Method.
本発明のメタノール合成方法によれば、触媒存在下でマイクロ波を照射し、触媒反応をマイクロ波による加熱状態で行わせることにより、マイクロ波と触媒との相乗効果によって、従来の触媒を使用したときよりも低温で二酸化炭素と水素からメタノールを合成できるので、より少ないエネルギーで二酸化炭素をメタノールに転化することができる。 According to the methanol synthesis method of the present invention, a conventional catalyst is used due to the synergistic effect of the microwave and the catalyst by irradiating the microwave in the presence of the catalyst and causing the catalytic reaction to be performed in a heated state by the microwave. Since methanol can be synthesized from carbon dioxide and hydrogen at lower temperatures than ever, carbon dioxide can be converted to methanol with less energy.
本発明の合成方法に用いるメタノール合成触媒は、銅酸化物、亜鉛酸化物およびランタン酸化物からなり、該ランタンの量が全触媒金属を基準として金属として０．５〜１０質量％である。ランタン含有量がこの範囲内にあると、メタノール転化率が高くなる。その理由は明らかではないが、触媒の塩基性が上がり、ＣＯ２の吸着量が増えたためと推察される。ランタン含有量は、好ましくは０．５〜５質量％、特に好ましくは０．７〜３質量％である。銅酸化物と亜鉛酸化物の比率は、両元素比で、銅：亜鉛＝９８：２〜３０：７０であることが好ましく、より好ましくは９０：１０〜３０：７０、特に好ましくは８０：２０〜６０：４０である。 The methanol synthesis catalyst used in the synthesis method of the present invention is composed of copper oxide, zinc oxide and lanthanum oxide, and the amount of lanthanum is 0.5 to 10% by mass based on the total catalyst metal. When the lanthanum content is within this range, the methanol conversion rate increases. The reason is not clear, but it is presumed that the basicity of the catalyst has increased and the amount of adsorption of CO 2 has increased. The lanthanum content is preferably 0.5 to 5% by mass, particularly preferably 0.7 to 3% by mass. The ratio of the copper oxide to the zinc oxide is preferably an element ratio of copper: zinc = 98: 2 to 30:70, more preferably 90:10 to 30:70, and particularly preferably 80:20. ~ 60: 40.
上記のメタノール合成触媒は、アルミニウムおよびガリウム、さらには銅、亜鉛の焼結防止のためのマグネシウム、バリウム、ストロンチウム、カルシウム等の添加は不要である。その理由は、本発明はより低温でより安価にメタノール合成することを目的としているため、焼結温度のような高温での反応は行わないためである。 The above methanol synthesis catalyst does not require the addition of magnesium, barium , strontium, calcium or the like to prevent sintering of aluminum and gallium, as well as copper and zinc. The reason is that the present invention aims to synthesize methanol at a lower temperature and at a lower cost, and therefore does not perform a reaction at a high temperature such as a sintering temperature.
本発明のメタノール合成方法に用いるメタノール合成触媒は、既知の方法に準じて製造することができるが、より高活性な触媒が得られ易いという点から、銅、亜鉛およびランタンの塩の水溶液から共沈法により製造することが好ましい。銅、亜鉛およびランタンの原料には、触媒毒を含まない硝酸塩、酢酸塩等の塩を使用するのが好ましく、特に硝酸塩が好ましい。前記の原料塩を水に溶かして、濃度０．０１〜１．０モル／Ｌの水溶液として用いる。 The methanol synthesis catalyst used in the methanol synthesis method of the present invention can be produced according to a known method. However, since a highly active catalyst can be easily obtained, the methanol synthesis catalyst is prepared from an aqueous solution of copper, zinc and lanthanum salts. It is preferable to manufacture by a precipitation method. As the raw materials for copper, zinc and lanthanum, it is preferable to use salts such as nitrates and acetates which do not contain catalyst poisons, and nitrates are particularly preferable. The raw material salt is dissolved in water and used as an aqueous solution having a concentration of 0.01 to 1.0 mol / L.
沈澱剤としては、沈澱率が高く高活性な触媒が得られることから、炭酸ナトリウムおよび重炭酸ナトリウムが好ましく、特に炭酸ナトリウムが好ましい。沈澱剤は水に溶かして、濃度０．０１〜１．０モル／Ｌの水溶液として用いる。 As the precipitant, sodium carbonate and sodium bicarbonate are preferable, and sodium carbonate is particularly preferable because a highly active catalyst having a high precipitation rate can be obtained. The precipitant is dissolved in water and used as an aqueous solution having a concentration of 0.01 to 1.0 mol / L.
例えば、沈澱剤水溶液を５０〜９０℃に加熱した後、保温し、撹拌しながら、沈澱剤水溶液に亜鉛硝酸塩の水溶液を滴下して懸濁液を得、次に銅硝酸塩の水溶液を懸濁液に滴下し、さらにランタン硝酸塩を滴下して沈殿物を生成する。これらの金属の硝酸塩を混合した水溶液を沈澱剤水溶液に滴下してもよい。滴下は連続して１分間〜４時間程度行い、その後、１時間〜４時間程度、撹拌、熟成する。沈澱物を濾過等により分離した後、Ｎａを除去するために十分水洗し、３００〜５００℃で焼成する。その後、Ｎ２、Ｈ２混合ガスにて還元して触媒を製造する。 For example, after heating a precipitant aqueous solution to 50 to 90 ° C., keeping it warm and stirring, an aqueous zinc nitrate solution is dropped into the precipitant aqueous solution to obtain a suspension, and then an aqueous copper nitrate solution is suspended. And lanthanum nitrate is added dropwise to form a precipitate. An aqueous solution in which these metal nitrates are mixed may be added dropwise to the aqueous precipitation agent solution. The dropping is continuously carried out for about 1 minute to 4 hours, and then stirred and aged for about 1 hour to 4 hours. After the precipitate is separated by filtration or the like, it is sufficiently washed with water to remove Na and calcined at 300 to 500 ° C. Thereafter, the catalyst is produced by reduction with a mixed gas of N 2 and H 2 .
本発明のメタノール合成方法においては、原料ガスとして、二酸化炭素と水素からなるガスを用いることが好ましいが、二酸化炭素は少なくとも二酸化炭素が含まれているガスであればよい。石炭、石油、ＬＮＧ、プラスチックの燃焼により生じた燃焼排ガスや、熱風炉排ガス、高炉排ガス、転炉排ガス、燃焼排ガス等の製鉄所副生ガスのような、二酸化炭素を１〜４０容量％含有する排ガス等も使用することができる。原料ガスには、窒素ガスなどの不活性ガスが含まれていてもよい。 In the methanol synthesis method of the present invention, it is preferable to use a gas composed of carbon dioxide and hydrogen as the raw material gas, but the carbon dioxide may be a gas containing at least carbon dioxide. Contains 1 to 40% by volume of carbon dioxide, such as combustion exhaust gas generated by combustion of coal, petroleum, LNG and plastics, and by-product gas of ironworks such as hot blast furnace exhaust gas, blast furnace exhaust gas, converter exhaust gas, and combustion exhaust gas Exhaust gas or the like can also be used. The source gas may contain an inert gas such as nitrogen gas.
二酸化炭素と水素の比率は、５０／５０〜５／９５（モル比）が好ましく、より好ましくは３０／７０〜８／９２（モル比）、特に好ましくは２０／８０〜１０／９０（モル比）である。二酸化炭素に対する水素の比率が高いほど、メタノール生成量が多くなるが、二酸化炭素の利用効率を考慮するとこの範囲が好ましい。 The ratio of carbon dioxide to hydrogen is preferably 50/50 to 5/95 (molar ratio), more preferably 30/70 to 8/92 (molar ratio), and particularly preferably 20/80 to 10/90 (molar ratio). ). The higher the ratio of hydrogen to carbon dioxide, the greater the amount of methanol produced, but this range is preferred in view of the utilization efficiency of carbon dioxide.
本発明のメタノール合成反応における反応温度は、１００〜３００℃が好ましく、特に好ましくは１５０〜２５０℃である。 100-300 degreeC is preferable and, as for the reaction temperature in the methanol synthesis reaction of this invention, Most preferably, it is 150-250 degreeC.
反応圧力は、常圧、加圧の何れでも良いが、通常、０．１ＭＰａ（常圧）〜３０ＭＰａである。反応ガスの流速は任意であるが、空間速度（ＳＶ）として２０００〜５００００ｈｒ−１が好ましい。 The reaction pressure may be normal pressure or increased pressure, but is usually 0.1 MPa (normal pressure) to 30 MPa. Although the flow rate of the reaction gas is arbitrary, the space velocity (SV) is preferably 2000 to 50000 hr −1 .
反応時間は、触媒量と反応温度に左右されて一定しないが、通常は反応進行状況を見ながら適宜に決定すればよい。 The reaction time depends on the amount of catalyst and the reaction temperature and is not constant, but usually it can be determined appropriately while observing the progress of the reaction.
照射するマイクロ波の出力や周波数、照射方法は、特に限定されるものではなく、反応温度が所定の範囲に保持できるよう電気的に制御すればよい。出力が低すぎる場合は反応の進行が遅くなり、出力が高すぎる場合はマイクロ波の利用率が悪くなる。マイクロ波の周波数は、通常、１ＧＨｚ〜３００ＧＨｚである。１ＧＨｚ未満又は３００ＧＨｚを超える周波数範囲では、反応促進効果が不十分となる。 The output, frequency, and irradiation method of the microwave to be irradiated are not particularly limited, and may be electrically controlled so that the reaction temperature can be maintained within a predetermined range. When the output is too low, the progress of the reaction is slow, and when the output is too high, the utilization rate of the microwave is deteriorated. The frequency of the microwave is usually 1 GHz to 300 GHz. In the frequency range below 1 GHz or above 300 GHz, the reaction promoting effect is insufficient.
マイクロ波の照射は連続照射、間欠照射のいずれの方法であってもよく、照射時間および照射停止時間は、反応用原料ガスあるいは反応触媒等に応じて適宜に決定すればよい。 The microwave irradiation may be either continuous irradiation or intermittent irradiation, and the irradiation time and irradiation stop time may be appropriately determined according to the reaction source gas or reaction catalyst.
本発明のメタノール合成方法では、触媒存在下において、触媒と二酸化炭素と水素とを接触させ、触媒にマイクロ波を照射することが好ましく、触媒が存在しない状態で該混合物にマイクロ波を照射しても、反応系の温度上昇が期待できず、また、反応速度は著しく遅くなる。中でも、二酸化炭素、水素及び触媒が十分接触するように、触媒を充填した触媒充填層を形成した触媒充填装置内に二酸化炭素及び水素からなるガスを導入し、二酸化炭素および水素を含む該触媒充填層へマイクロ波を照射する方法が、エネルギー効率的に最も好ましい。この方法によれば、ヒーター等の加熱手段と異なり、マイクロ波が触媒に当ることによって触媒表面が優先的に活性化されるので、エネルギー利用効率を著しく高めることが可能となる。 In the methanol synthesis method of the present invention, it is preferable that the catalyst, carbon dioxide and hydrogen are brought into contact with each other in the presence of the catalyst, and the catalyst is irradiated with microwaves. In the absence of the catalyst, the mixture is irradiated with microwaves. However, the temperature rise of the reaction system cannot be expected, and the reaction rate is remarkably slow. In particular, a gas comprising carbon dioxide and hydrogen is introduced into a catalyst filling device in which a catalyst packed bed filled with a catalyst is formed so that carbon dioxide, hydrogen and the catalyst are in sufficient contact, and the catalyst filling containing carbon dioxide and hydrogen is performed. The method of irradiating the layer with microwaves is most preferable in terms of energy efficiency. According to this method, unlike the heating means such as a heater, the catalyst surface is preferentially activated by the microwaves striking the catalyst, so that the energy utilization efficiency can be remarkably increased.
以下、本発明の実施例について図面を参照して説明するが、本発明は以下の実施例にのみ限定されるものではない。 Hereinafter, examples of the present invention will be described with reference to the drawings. However, the present invention is not limited to the following examples.
（触媒製造例１）
１０００ｍｌの水に、８５．４１ｇの試薬特級硝酸銅・３水和物、４３．５７ｇの試薬特級硝酸亜鉛・６水和物、および２．２８ｇの試薬特級硝酸ランタン・６水和物を溶解させた金属塩水溶液を調製し８０℃に加温した。別に、１０００ｍｌの純水に５３．４８ｇの試薬特級炭酸ナトリウムを含む水溶液を調製し６０℃に加温した。上記の金属塩水溶液を撹拌しながら該水溶液中に、上記の炭酸ナトリウム水溶液を１０ｍｌ／ｍｉｎで滴下し沈澱を生成させた。ｐＨが９．０になった時点で、炭酸ナトリウム水溶液の滴下をやめ、その後、撹拌下に液温を８０℃に２時間保った後、さらに８０℃のまま２時間静置し熟成させた。その後沈澱を濾過、洗浄し、８０℃で一晩乾燥してから、乾燥物を乳鉢にて粉砕し、２ｗｔ％のグラファイト粉末（バインダー）を添加し、１時間混和した。
上記混合物を圧力５ｋＮにて一軸加圧成型器を用いて成型した後、成型物をマッフル炉（電気炉）を用いて、３５０℃で３時間空気を流通させながら焼成した。昇温速度は３℃／ｍｉｎとした。
焼成した触媒は、窒素雰囲気下で２３０℃まで昇温（昇温速度３℃／ｍｉｎ）し、ついで水素：窒素＝１：９のガスにて２３０℃、３時間還元した。
この触媒を触媒Ａとした。
(Catalyst production example 1)
Dissolve 85.41g reagent grade copper nitrate trihydrate, 43.57g reagent grade zinc nitrate hexahydrate, and 2.28g reagent grade lanthanum nitrate hexahydrate in 1000ml water. An aqueous metal salt solution was prepared and heated to 80 ° C. Separately, an aqueous solution containing 53.48 g of reagent-grade sodium carbonate in 1000 ml of pure water was prepared and heated to 60 ° C. While stirring the aqueous metal salt solution, the aqueous sodium carbonate solution was dropped into the aqueous solution at 10 ml / min to form a precipitate. When the pH reached 9.0, dropping of the sodium carbonate aqueous solution was stopped, and then the liquid temperature was maintained at 80 ° C. for 2 hours with stirring, and then the mixture was further left to stand for 2 hours at 80 ° C. for aging. Thereafter, the precipitate was filtered and washed, dried at 80 ° C. overnight, the dried product was pulverized in a mortar, 2 wt% graphite powder (binder) was added, and the mixture was mixed for 1 hour.
The mixture was molded using a uniaxial pressure molding machine at a pressure of 5 kN, and the molded product was fired using a muffle furnace (electric furnace) at 350 ° C. for 3 hours while circulating air. The heating rate was 3 ° C./min.
The calcined catalyst was heated to 230 ° C. under a nitrogen atmosphere (temperature rising rate: 3 ° C./min), and then reduced at 230 ° C. for 3 hours with a gas of hydrogen: nitrogen = 1: 9.
This catalyst was designated as Catalyst A.
（触媒製造例２）
試薬特級硝酸亜鉛・６水和物を４０．５７ｇ、試薬特級硝酸ランタン・６水和物を６．８４ｇ用い、目標ｐＨを８．８５とした以外は、触媒製造例１と同様の方法にて触媒Ｂを製造した。
(Catalyst production example 2)
Using the same method as in Catalyst Production Example 1, except that 40.57 g of reagent-grade zinc nitrate hexahydrate, 6.84 g of reagent-grade lanthanum nitrate hexahydrate were used, and the target pH was 8.85. Catalyst B was prepared.
（触媒製造例３）
試薬特級硝酸亜鉛・６水和物を３７．５８ｇ、試薬特級硝酸ランタン・６水和物を１１．４０ｇ用い、目標ｐＨを８．７７とした以外は、触媒製造例１と同様の方法にて触媒Ｃを製造した。
(Catalyst production example 3)
The same method as in Catalyst Production Example 1 except that 37.58 g of reagent-grade zinc nitrate hexahydrate, 11.40 g of reagent-grade lanthanum nitrate hexahydrate were used, and the target pH was 8.77. Catalyst C was prepared.
（触媒製造例４）
試薬特級硝酸亜鉛・６水和物を３０．０５ｇ、試薬特級硝酸ランタン・６水和物を２２．７９ｇ用い、目標ｐＨを８．６７とした以外は、触媒製造例１と同様の方法にて触媒Ｄを製造した。
(Catalyst production example 4)
Using the same method as in Catalyst Production Example 1, except that 30.05 g of reagent-grade zinc nitrate hexahydrate, 22.79 g of reagent-grade lanthanum nitrate hexahydrate were used, and the target pH was 8.67. Catalyst D was prepared.
（比較製造例１）
試薬特級硝酸亜鉛・６水和物を４５．０７ｇ用い、試薬特級硝酸ランタン・６水和物は用いず、目標ｐＨを７．７１としたこと以外は、触媒製造例１と同様の方法にて触媒Ｅを製造した。
(Comparative Production Example 1)
Using the same method as in Catalyst Production Example 1, except that 45.07 g of reagent-grade zinc nitrate hexahydrate was used, reagent-grade lanthanum nitrate hexahydrate was not used, and the target pH was 7.71. Catalyst E was prepared.
（実施例１）
特願２００７−０５９３２２明細書に記載の固定床流通式の触媒活性評価装置を用いて試験した。図１に系統図を示す。
反応は外径７５ｍｍΦ、高さ１２０ｍｍの円筒型ステンレス（ＳＵＳ）製反応容器３を使用し、反応容器３内には、高さ５０ｍｍの原料ガスバッファー部３５を設け、ステンレスのクラッドを３ヶ所削り、内径１０ｍｍΦ、高さ約５０ｍｍ、内容量約４ｃｍ３の触媒設置部３１を均等に３個配置した。触媒設置部３１の中に、１ｍｍ〜２ｍｍに調整した触媒約１ｇを充填した。反応容器の周囲をマントルヒーター３２にて覆い、温度コントローラを用いて加熱温度を制御した。反応容器３は、密閉式であり、底面に温度測定座を設けた。
Example 1
It tested using the fixed bed flow-type catalyst activity evaluation apparatus as described in Japanese Patent Application No. 2007-059322 specification. A system diagram is shown in FIG.
For the reaction, a cylindrical stainless steel (SUS) reaction vessel 3 having an outer diameter of 75 mmΦ and a height of 120 mm was used. In the reaction vessel 3, a raw material gas buffer unit 35 having a height of 50 mm was provided, and the stainless clad was cut in three places. Three catalyst installation portions 31 having an inner diameter of 10 mmΦ, a height of about 50 mm, and an internal volume of about 4 cm 3 were arranged uniformly. About 1 g of the catalyst adjusted to 1 mm to 2 mm was filled in the catalyst installation part 31. The periphery of the reaction vessel was covered with a mantle heater 32, and the heating temperature was controlled using a temperature controller. The reaction vessel 3 was hermetically sealed and provided with a temperature measurement seat on the bottom surface.
また、原料ガス又はパージ用ガスを収容したボンベと、反応容器３は、内径６ｍｍのステンレス（ＳＵＳ）製チューブを用いて接続した。なお、テフロン（登録商標）またはガラス製のチューブを用いて接続することも可能である。 The cylinder containing the raw material gas or the purge gas and the reaction vessel 3 were connected using a stainless steel (SUS) tube having an inner diameter of 6 mm. It is also possible to connect using a Teflon (registered trademark) or glass tube.
原料ガス及びパージ用ガスの流量制御は圧力調整弁１にて行い、途中に、パージガス用
仕切弁２と、水素還元用ガス切替用の三方弁６を設置した。反応容器の後流には、反応容
器から導出されたガスの流量調整弁５、流量計１０を設け、評価時に触媒設置部における
原料ガスの空間速度を統一するようにした。触媒ごとに導出された生成ガスに含まれるメ
タノール濃度を、ガスクロマトグラフにて測定した。
The flow rate control of the source gas and the purge gas was performed by the pressure regulating valve 1, and a purge gas gate valve 2 and a three-way valve 6 for switching the hydrogen reduction gas were installed on the way. The flow rate adjusting valve 5 and the flow meter 10 for the gas led out from the reaction vessel are provided in the downstream of the reaction vessel, and the space velocity of the raw material gas in the catalyst installation portion is unified during the evaluation. The concentration of methanol contained in the product gas derived for each catalyst was measured with a gas chromatograph.
水素還元用ガスは、評価触媒の前処理用として使用できるように収容パック１４に収容
し、そのガスを循環ポンプ１５にて循環させた。触媒の前処理時は、水素還元用ガス切替
用の三方弁６、７、８及びパージ用仕切弁１６を操作し、評価触媒にのみ水素還元用ガス
を循環させ、途中に触媒調整時に発生する水のトラップ１３を設けた。
The hydrogen reduction gas was stored in the storage pack 14 so that it could be used for pretreatment of the evaluation catalyst, and the gas was circulated by the circulation pump 15. During catalyst pretreatment, the three-way valves 6, 7, 8 for switching the hydrogen reducing gas and the purge gate valve 16 are operated to circulate the hydrogen reducing gas only to the evaluation catalyst, and this occurs during catalyst adjustment in the middle. A water trap 13 was provided.
上記装置より反応容器を取り外し、触媒製造例で作製したＣｕＯ−ＺｎＯ−Ｌａ２Ｏ３系触媒（触媒Ａ〜Ｄ，Ｅ）約１ｇを反応容器内にセットし、反応容器を装置にセットした。 The reaction container was removed from the apparatus, about 1 g of CuO—ZnO—La 2 O 3 catalyst (catalysts A to D, E) prepared in the catalyst production example was set in the reaction container, and the reaction container was set in the apparatus.
１０Ｌテドラーパック１４に、水素還元用ガス（Ｈ２＋Ｎ２）を封入し、装置にセットした。三方弁（水素還元切替）６及び７を水素還元ラインに切り替え、ガス循環ポンプ１５をＯＮにした。各ラインの流量調整弁５にて流量計１０を所定流量に調整した。温度制御装置を水素還元温度にセットし、加熱を開始した。設定還元温度となってから、所定時間保持した。 Hydrogen reduction gas (H 2 + N 2 ) was sealed in a 10 L tedlar pack 14 and set in the apparatus. The three-way valves (hydrogen reduction switching) 6 and 7 were switched to the hydrogen reduction line, and the gas circulation pump 15 was turned on. The flow meter 10 was adjusted to a predetermined flow rate by the flow rate adjustment valve 5 of each line. The temperature controller was set to the hydrogen reduction temperature and heating was started. After reaching the set reduction temperature, it was held for a predetermined time.
温度制御装置スイッチをＯＦＦにし、ある程度温度が下がったところで、三方弁（パージ切替）８をガス排気ラインに切り替え、パージ用仕切弁１６を開けて（Ｈ２＋Ｎ２）混合ガスを排気した。全量排気が終了したら、ガス循環ポンプ１５を停止した。三方弁（水素還元切替）６を活性試験ラインに切り替えた。パージガス用仕切弁２を開けて、窒素ボンベからガスを反応系内に導入し、約１０ｍｉｎ、窒素で反応系内をパージした。 When the temperature control device switch was turned off and the temperature dropped to some extent, the three-way valve (purge switching) 8 was switched to the gas exhaust line, the purge gate valve 16 was opened (H 2 + N 2 ), and the mixed gas was exhausted. When exhausting the entire amount, the gas circulation pump 15 was stopped. The three-way valve (hydrogen reduction switching) 6 was switched to the activity test line. The purge gas gate valve 2 was opened, gas was introduced into the reaction system from a nitrogen cylinder, and the reaction system was purged with nitrogen for about 10 minutes.
パージガス用仕切弁２を閉じ、窒素ボンベの元栓を閉めた。ＣＯ２＋Ｈ２混合ガス（ＣＯ２／Ｈ２＝２０／８０）のボンベを開放し、原料ガスを導入した。圧力調整弁１で反応圧力条件（０．３ＭＰａ）に合わせた。温度制御装置を反応温度にセットし、加熱を開始した。原料ガスをサンプリング口（反応前）１１よりマイクロシリンジで採取し、ガスクロマトグラフィーにて反応前のガス組成を確認した。設定温度到達後、三方弁（水素還元切替）７をサンプリング座側に切替え、ガスを流し一定時間ごとに反応ガスをサンプリング口１２よりマイクロシリンジで採取し、ガスクロマトグラフにて反応後のガス組成を確認した。 The purge gas gate valve 2 was closed, and the main stopper of the nitrogen cylinder was closed. The cylinder of CO 2 + H 2 mixed gas (CO 2 / H 2 = 20/80) was opened, and the raw material gas was introduced. The pressure was adjusted to the reaction pressure condition (0.3 MPa) with the pressure regulating valve 1. The temperature controller was set to the reaction temperature and heating was started. The raw material gas was collected from the sampling port (before the reaction) 11 with a microsyringe, and the gas composition before the reaction was confirmed by gas chromatography. After reaching the set temperature, the three-way valve (hydrogen reduction switching) 7 is switched to the sampling seat side, the gas is flowed, the reaction gas is sampled from the sampling port 12 with a microsyringe at regular intervals, and the gas composition after reaction is measured by a gas chromatograph. confirmed.
温度制御装置のスイッチをＯＦＦにし、ＣＯ２＋Ｈ２混合ガスボンベの元栓を閉じた。窒素ボンベの元栓を開けて、反応系内を窒素でパージした。温度が下がったら、窒素ボンベの元栓、パージ用仕切弁１６を閉じた。 The switch of the temperature control device was turned off, and the main plug of the CO 2 + H 2 gas mixture cylinder was closed. The main stopper of the nitrogen cylinder was opened, and the inside of the reaction system was purged with nitrogen. When the temperature dropped, the main stopper of the nitrogen cylinder and the purge gate valve 16 were closed.
生成したメタノール量から、下記式よりメタノール空時収量を求めた。その結果を表１に示した。 From the amount of methanol produced, the methanol space time yield was determined from the following formula. The results are shown in Table 1.
メタノール空時収量(g/kg-cat・h)＝メタノール生成量／（触媒設置重量×反応時間） Methanol space time yield (g / kg-cat · h) = amount of methanol produced / (weight of catalyst installed x reaction time)
表１に示すように、本発明のメタノール合成触媒は、Ｌａ１％組成での活性が最も良かった。 As shown in Table 1, the methanol synthesis catalyst of the present invention had the best activity at a La 1% composition.
（実施例２）
触媒として、ＣｕＯ−ＺｎＯ−Ｌａ２Ｏ３触媒（触媒Ａ、Ｃ、Ｄ）を用い、相対圧を０．０２〜１．００まで変化させて触媒への二酸化炭素（ＣＯ２）の吸着実験を行った。その結果を表２に示した。なお、実験は定容吸着法に準じて実施し、高速・比表面積・細孔分布測定装置（Quantachrome社製、Nova1200e）を用いて、ＣＯ２吸着量の測定を実施した。表２に示すように、圧力が高くなるほど二酸化炭素（ＣＯ２）の吸着量も増えるが、Ｌａ１％組成での吸着量が最も高かった。
(Example 2)
Using a CuO—ZnO—La 2 O 3 catalyst (catalysts A, C, D) as a catalyst, and changing the relative pressure from 0.02 to 1.00, carbon dioxide (CO 2 ) adsorption experiment on the catalyst went. The results are shown in Table 2. The experiment was carried out according to the constant volume adsorption method, and the CO 2 adsorption amount was measured using a high speed, specific surface area / pore distribution measuring device (manufactured by Quantachrome, Nova1200e). As shown in Table 2, the amount of adsorption of carbon dioxide (CO 2 ) increased as the pressure increased, but the amount of adsorption at the La 1% composition was the highest.
（実施例３）
触媒としてＣｕＯ−ＺｎＯ−Ｌａ２Ｏ３触媒（触媒Ａ）６０ｇを用い、反応温度を１５０℃、１６０℃、１７０℃、１８０℃、２００℃、反応圧力０．８ＭＰａ、ガス（ＣＯ２／Ｈ２＝２０／８０）、流量３Ｌ／ｍｉｎ、反応時間２時間にて、２段式マイクロ波反応装置によりメタノール合成反応を行った。このときのＳＶ値は３３００ｈ−１であった。反応中のマイクロ波の電力量は０．４４ｋＷｈであった。
反応後、実施例１同様、生成ガスと液体を分析し同定・定量した後、生成したメタノール量から下記式よりメタノール転化率を求めた。
(Example 3)
As the catalyst, 60 g of CuO—ZnO—La 2 O 3 catalyst (catalyst A) was used, the reaction temperature was 150 ° C., 160 ° C., 170 ° C., 180 ° C., 200 ° C., the reaction pressure was 0.8 MPa, and the gas (CO 2 / H 2 = 20/80), a flow rate of 3 L / min, and a reaction time of 2 hours, a methanol synthesis reaction was performed using a two-stage microwave reactor. The SV value at this time was 3300 h −1 . The amount of microwave power during the reaction was 0.44 kWh.
After the reaction, as in Example 1, the product gas and liquid were analyzed, identified and quantified, and the methanol conversion rate was determined from the following formula from the amount of methanol produced.
メタノール転化率（％）＝メタノール生成量（ｍｏｌ）／ＣＯ２（ｍｏｌ）×１００ Methanol conversion (%) = methanol production (mol) / CO 2 (mol) × 100
結果を表３に示した。 The results are shown in Table 3.
（比較例１）
触媒としてＣｕＯ−ＺｎＯ触媒（日揮化学Ｎ２１１、ＣｕＯ：ＺｎＯ＝５２：４８）８０ｇを用い、反応温度を１８０℃、２００℃、２１０℃、２２０℃、２３０℃にした以外は、実施例３と同様な方法によりメタノール合成反応を行った。なお、触媒重量は実施例３での触媒ＡにおけるＳＶ値（ＳＶ＝３３００ｈ−１）と合わせた。反応中のマイクロ波の電力量は０．６１ｋＷｈであった。
反応後、実施例１同様、生成ガスと液体を分析し同定・定量した後、生成したメタノール量からメタノール転化率を求めた。その結果を表３に示した。
(Comparative Example 1)
Example 3 except that 80 g of CuO—ZnO catalyst (JGC Chemical N211, CuO: ZnO = 52: 48) was used as the catalyst, and the reaction temperatures were 180 ° C., 200 ° C., 210 ° C., 220 ° C., 230 ° C. The methanol synthesis reaction was carried out by various methods. The catalyst weight was combined with the SV value (SV = 3300 h −1 ) for catalyst A in Example 3. The amount of microwave power during the reaction was 0.61 kWh.
After the reaction, as in Example 1, the product gas and liquid were analyzed, identified and quantified, and then the methanol conversion was determined from the amount of methanol produced. The results are shown in Table 3.
表３に示すように、本発明の触媒は従来の触媒に比べてメタノールへの転化率が高く、また、１６０℃付近で最適な反応温度となり、反応が低温側にシフトしたことがわかった。 As shown in Table 3, it was found that the catalyst of the present invention had a higher conversion rate to methanol than the conventional catalyst, and reached an optimum reaction temperature near 160 ° C., and the reaction shifted to the low temperature side.
１ 圧力調整弁
２ パージガス用仕切弁
３ 反応容器
３１ 触媒設置部
３２ ヒーター
３３ 原料ガス導入部
３４ 反応ガス導出部
３５ バッファー部
４ ガス検知管
５ 流量調整弁
６ 三方弁（水素還元切替）
７ 三方弁（水素還元切替）
８ 三方弁（パージ切替）
９ 圧力計
１０ 流量計
１１ サンプリング口（反応前）
１２ サンプリング口（反応後）
１３ 水トラップ
１４ 水素還元用バッファーガス
１５ ガス循環ポンプ
１６ パージ用仕切弁
DESCRIPTION OF SYMBOLS 1 Pressure control valve 2 Purge gas gate valve 3 Reaction container 31 Catalyst installation part 32 Heater 33 Raw material gas introduction part 34 Reaction gas derivation part 35 Buffer part 4 Gas detection pipe 5 Flow control valve 6 Three-way valve (hydrogen reduction switching)
7 Three-way valve (hydrogen reduction switching)
8 Three-way valve (purge switching)
9 Pressure gauge 10 Flow meter 11 Sampling port (before reaction)
12 Sampling port (after reaction)
13 Water trap 14 Hydrogen reduction buffer gas 15 Gas circulation pump 16 Purge gate valve
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008063249A JP5303971B2 (en) | 2008-03-12 | 2008-03-12 | Methanol synthesis method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008063249A JP5303971B2 (en) | 2008-03-12 | 2008-03-12 | Methanol synthesis method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2009215263A JP2009215263A (en) | 2009-09-24 |
| JP5303971B2 true JP5303971B2 (en) | 2013-10-02 |
Family
ID=41187504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008063249A Expired - Fee Related JP5303971B2 (en) | 2008-03-12 | 2008-03-12 | Methanol synthesis method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5303971B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5541055B2 (en) * | 2010-10-01 | 2014-07-09 | 東京電力株式会社 | Methanol synthesis catalyst and methanol synthesis method |
| CN105498780B (en) * | 2015-12-24 | 2018-01-23 | 大连工业大学 | A kind of Cu/ZnO catalyst and preparation method thereof and in CO2Application in chemical conversion |
| JP7349111B1 (en) | 2023-03-08 | 2023-09-22 | 株式会社アビット・テクノロジーズ | Reduction reaction device and method for producing a reduced product of a compound to be treated |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5426983A (en) * | 1977-08-02 | 1979-02-28 | Mitsubishi Gas Chem Co Inc | Methanol synthesis catalyst |
| JP3259020B2 (en) * | 1991-08-21 | 2002-02-18 | 智行 乾 | Oxide-based catalyst, method for producing the same, and method for catalytic hydrogenation of CO2 using the catalyst |
| JPH08215570A (en) * | 1995-02-17 | 1996-08-27 | Ykk Kk | Catalyst for synthesis of methanol, production thereof and synthesis of methanol |
| JP3510405B2 (en) * | 1995-11-22 | 2004-03-29 | 三菱重工業株式会社 | Methanol synthesis catalyst |
| JP3943648B2 (en) * | 1997-04-11 | 2007-07-11 | 関西電力株式会社 | Methanol synthesis method |
| JP5205693B2 (en) * | 2004-11-17 | 2013-06-05 | 東京電力株式会社 | Method for immobilizing CO2 using microwaves |
| JP2007261960A (en) * | 2006-03-01 | 2007-10-11 | Tokyo Electric Power Co Inc:The | Method for continuously producing higher fatty acid methyl ester from co2 |
| JP4905849B2 (en) * | 2006-04-07 | 2012-03-28 | 東京電力株式会社 | Synthesis method of dimethyl ether using microwave |
-
2008
- 2008-03-12 JP JP2008063249A patent/JP5303971B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2009215263A (en) | 2009-09-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Alipour et al. | Effects of support modifiers on the catalytic performance of Ni/Al2O3 catalyst in CO2 reforming of methane | |
| Wierzbicki et al. | Ni-Fe layered double hydroxide derived catalysts for non-plasma and DBD plasma-assisted CO2 methanation | |
| Vita et al. | Biogas as renewable raw material for syngas production by tri-reforming process over NiCeO2 catalysts: Optimal operative condition and effect of nickel content | |
| Song et al. | Methanol steam reforming for hydrogen production over ternary composite ZnyCe1Zr9Ox catalysts | |
| Vita et al. | Influence of Ce-precursor and fuel on structure and catalytic activity of combustion synthesized Ni/CeO2 catalysts for biogas oxidative steam reforming | |
| Jiang et al. | Chemical looping glycerol reforming for hydrogen production by Ni@ ZrO2 nanocomposite oxygen carriers | |
| Monteiro et al. | Dry reforming of methane using modified sodium and protonated titanate nanotube catalysts | |
| Valverde et al. | Limestone calcination under calcium-looping conditions for CO 2 capture and thermochemical energy storage in the presence of H 2 O: an in situ XRD analysis | |
| Chen et al. | Assessment of the effect of process conditions and material characteristics of alkali metal salt promoted MgO-based sorbents on their CO2 capture performance | |
| Ni et al. | High purity hydrogen production from sorption enhanced chemical looping glycerol reforming: Application of NiO-based oxygen transfer materials and potassium promoted Li2ZrO3 as CO2 sorbent | |
| TW200836833A (en) | Catalyst for carbon monoxide conversion and method of carbon monoxide modification with the same | |
| Meshkani et al. | Ni catalysts supported on nanocrystalline magnesium oxide for syngas production by CO2 reforming of CH4 | |
| CN106694008B (en) | With support type RhNi/CeO2@C3N4The method of nanocatalyst Compounds with Hydrazine Hydrate Catalyzed dehydrogenation | |
| JP3005647B2 (en) | Photocatalyst, method for producing the same, and method for producing hydrogen using the same | |
| JP5303971B2 (en) | Methanol synthesis method | |
| Richard et al. | The effect of lanthanide promoters on NiInAl/SiO2 catalyst for methanol synthesis | |
| KR20140087264A (en) | Mesoporous Ni-X-Al2O3 xerogel catalyst, preparation method thereof, and method for preparing methane using said catalyst | |
| JP2008036451A (en) | Catalyst support and catalyst for methane reformation and method for preparing the same | |
| JP2006216412A (en) | Microwave heating device and carbon dioxide decomposition method using it | |
| Li et al. | Continuous CO 2 capture and methanation over Ni–Ca/Al 2 O 3 dual functional materials | |
| Oliveira et al. | Hydrogen production from sorption enhanced steam reforming of ethanol using bifunctional Ni and Ca-based catalysts doped with Mg and Al | |
| Ranjekar et al. | Hydrogen production by steam reforming of methanol by Cu–Zn/CeAlO 3 perovskite | |
| Zyryanova et al. | Selective methanation of CO in the presence of CO 2 in hydrogen-containing mixtures on nickel catalysts | |
| JP5374955B2 (en) | Method for synthesizing methanol from carbon dioxide | |
| JP2003038957A (en) | Catalyst for reforming dimethyl ether and method for producing hydrogen containing gas using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20110107 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20120720 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120731 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120928 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20130528 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130610 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 5303971 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| LAPS | Cancellation because of no payment of annual fees |