JP2022016242A - Iron-based fischer-tropsch synthesis catalyst, and method for preparing the same - Google Patents

Iron-based fischer-tropsch synthesis catalyst, and method for preparing the same Download PDF

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JP2022016242A
JP2022016242A JP2020183688A JP2020183688A JP2022016242A JP 2022016242 A JP2022016242 A JP 2022016242A JP 2020183688 A JP2020183688 A JP 2020183688A JP 2020183688 A JP2020183688 A JP 2020183688A JP 2022016242 A JP2022016242 A JP 2022016242A
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鮑周艶
Zhou Yan Bao
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    • C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group

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Abstract

To provide an iron-based Fischer-Tropsch synthesis catalyst having high catalytic activity, high selectivity of a target product, excellent sintering resistance, and high stability.SOLUTION: An iron-based Fischer-Tropsch synthesis catalyst containing 20% to 30% of metal iron and the balance carbon, in which the carbon is prepared by nano-polyacrylamide, citric acid and amino acid, and the catalyst can contain any auxiliary component in addition to active ingredient iron and carrier carbon. For example, rare earth oxide such as cerium oxide and lanthanum oxide, transition metal oxide such as manganese oxide, chromium oxide and rhenium oxide, and alkali earth metal oxide such as magnesium oxide are cited. It is preferable that the content of auxiliary component be 0.5 to 5wt% by using the total weight of catalyst as a reference.SELECTED DRAWING: Figure 1

Description

本発明は触媒の分野に属し、具体的には鉄基フィッシャー・トロプシュ合成触媒及びその調製方法に関する。 The present invention belongs to the field of catalysts, and specifically relates to an iron-based Fischer-Tropsch synthesis catalyst and a method for preparing the same.

フィッシャー・トロプシュ反応（Ｆｉｓｃｈｅｒ‐Ｔｒｏｐｓｃｈｓｙｎｔｈｅｓｉｓ、略称ＦＴＳ）はカイザー・ウィルヘルム研究所に勤務していたドイツの研究者、フランツ・フィッシャー（Ｆｒａｎｚ Ｆｉｓｃｈｅｒ）とハンス・トロプシュ（Ｈａｎｓ Ｔｒｏｐｓｃｈ）によって１９２０年代に開発されたのが起源である。触媒としては鉄やコバルトの化合物が一般的である。この方法の主な目的は、石油の代替品となる合成油や合成燃料を作り出すことである。「フィッシャー・トロプシュ反応」や「フィッシャー・トロプシュ合成」とも呼ばれる。この反応は、石油資源が不足する現状を緩和するだけでなく、石炭や天然ガスやバイオマスなどの資源の効率的な利用が可能となる。我が国のエネルギー分布は「石炭に富み、石油に貧しく、天然ガスに貧しい」であり、石炭の採掘期は石油を遥かに超えるが、中国の大部分の石炭はそのまま燃焼して利用され、環境を深刻に汚染するＳＯ２、ＮＯｘ等の物質が放出される。資源利用及び環境保護の観点から見れば、石炭代替燃料及び非石油ルートを開発して高付加価値の化学工業製品を調製することは大きな市場将来性及び重要な戦略的意義を有する。 The Fischer-Tropsch synthesis (FTS) was developed in the 1920s by German researchers Franz Fisher and Hans Tropsch, who worked at the Kaiser Wilhelm Institute. Is the origin. As a catalyst, a compound of iron or cobalt is generally used. The main purpose of this method is to produce synthetic oils and fuels that are alternatives to petroleum. Also called "Fischer-Tropsch reaction" or "Fischer-Tropsch synthesis". This reaction not only alleviates the current shortage of petroleum resources, but also enables efficient use of resources such as coal, natural gas and biomass. Japan's energy distribution is "rich in coal, poor in oil, poor in natural gas", and although the mining period of coal far exceeds that of oil, most of China's coal is burned and used as it is, creating an environment. Seriously contaminated substances such as SO 2 and NO x are released. From the viewpoint of resource utilization and environmental protection, developing coal alternative fuels and non-petroleum routes to prepare high value chemical industry products has great market potential and important strategic significance.

フィッシャー・トロプシュ合成触媒は一般的に鉄基フィッシャー・トロプシュ合成触媒、コバルト系フィッシャー・トロプシュ合成触媒及びルテニウム系フィッシャー・トロプシュ合成触媒を含む。フィッシャー・トロプシュ合成反応において、選択性に影響を及ぼす重要な要素の一つは触媒の選択であり、触媒の調製方法を改善することは目標生成物の選択性を明らかに向上させることができる。 Fischer-Tropsch synthesis catalysts generally include iron-based Fischer-Tropsch synthesis catalysts, cobalt-based Fischer-Tropsch synthesis catalysts and ruthenium-based Fischer-Tropsch synthesis catalysts. In the Fischer-Tropsch synthesis reaction, one of the important factors affecting the selectivity is the selection of the catalyst, and improving the method of preparing the catalyst can clearly improve the selectivity of the target product.

ＣＮ１３９８６６９Ａには、コバルト・ジルコニウムフィッシャートロプシュ合成触媒に関するものが開示されていますが、重量百分率でコバルト１０．０～８０．０％、酸化ジルコニウムは１５．０～８５．０％、金属酸化物助剤０～５．０％を含み、前記金属酸化物助剤は酸化セリウム、酸化マンガン等である。担体としてジルコニアを用い、フィッシャー・トロプシュ合成の反応条件ではコバルトとジルコニアとの間に化合物が形成されないため、触媒は安定性に優れ、失活レートが低く、高い還元度及び金属分散度を有する。しかし、この触媒は、通常の還元温度（４２０℃程度）で還元する必要があり、これにより、調製過程で必要なエネルギー消費を高める他、担体のセル構造を破壊しやすい。 CN1398669A discloses a cobalt-zirconium Fishertropush synthesis catalyst, which is 10.0 to 80.0% by weight of cobalt, 15.0 to 85.0% of zirconium oxide, and a metal oxide aid. The metal oxide auxiliary agent contains 0 to 5.0%, and the metal oxide auxiliary is cerium oxide, manganese oxide, or the like. Since zirconia is used as a carrier and no compound is formed between cobalt and zirconia under the reaction conditions of Fischer-Tropsch synthesis, the catalyst has excellent stability, a low deactivation rate, and a high degree of reduction and metal dispersion. However, this catalyst needs to be reduced at a normal reduction temperature (about 420 ° C.), which increases the energy consumption required in the preparation process and easily destroys the cell structure of the carrier.

ＵＳ５７３３８８９Ａには、Ｐｔを助剤とし、Ａｌ２Ｏ２を担体とするコバルト系フィッシャー・トロプシュ合成触媒に関するものが開示されていますが、ＰｔとＣｏの重量比が（０．００００５‐０．１）：１である。この触媒は、高い触媒活性を有するものの、貴金属Ｐｔが導入されているため、触媒の生産コストが高くなっている。 US5733889A discloses a cobalt-based Fischer-Tropsch synthesis catalyst using Pt as an auxiliary agent and Al2O2 as a carrier, but the weight ratio of Pt to Co is (0.00005-0.1): 1. be. Although this catalyst has high catalytic activity, the production cost of the catalyst is high because the precious metal Pt is introduced.

中国特許出願公開第１１００７５８４４号明細書Chinese Patent Application Publication No. 110075844

本発明は、上記課題を解決するために、鉄基フィッシャー・トロプシュ合成触媒及びその調製方法を提供することを目的とする。 An object of the present invention is to provide an iron-based Fischer-Tropsch synthesis catalyst and a method for preparing the same, in order to solve the above problems.

鉄基フィッシャー・トロプシュ合成触媒であって、２０％～３０％の金属鉄と、残部の炭素とを含む。前記炭素はナノポリアクリルアミド、クエン酸及びアミノ酸で調製される。 An iron-based Fischer-Tropsch synthesis catalyst containing 20% to 30% metallic iron and the balance of carbon. The carbon is prepared with nanopolyacrylamide, citric acid and amino acids.

本発明における鉄基フィッシャー・トロプシュ合成触媒は、活性成分鉄及び担体炭素に加えて、任意の助剤成分を含有することができる。例えば、酸化セリウム、酸化ランタン等の希土類酸化物、酸化マンガン、酸化クロム、酸化レニウム等の遷移金属酸化物、酸化マグネシウム等のアルカリ土類金属酸化物が挙げられる。助剤成分の含有量は、触媒の全重量を基準として０．５～５ｗｔ％であることが好ましい。 The iron-based Fischer-Tropsch synthesis catalyst in the present invention can contain any auxiliary component in addition to the active ingredient iron and carrier carbon. Examples thereof include rare earth oxides such as cerium oxide and lanthanum oxide, transition metal oxides such as manganese oxide, chromium oxide and renium oxide, and alkaline earth metal oxides such as magnesium oxide. The content of the auxiliary agent component is preferably 0.5 to 5 wt% based on the total weight of the catalyst.

鉄基フィッシャー・トロプシュ合成触媒の調製方法であって、ステップ１からステップ４で調製され、
前記ステップ１は、四酸化三鉄又は酸化鉄を脱イオン水に分散し、クエン酸を加え、８０℃に昇温して四酸化三鉄又は酸化鉄が完全に溶解するまで撹拌し、冷却して不溶性不純物を濾過し、濾過後、濾液にアンモニア水を加えて酸塩基性を調整し、ｐＨを３～４にし、そして８５℃に昇温した後、３ｈ撹拌を続け、クエン酸鉄錯体を形成し、使用に備える。
前記ステップ２は、ナノポリアクリルアミドを脱イオン水に分散し、アミノ酸を加え、９０℃に昇温し、２ｈ撹拌し、アミノ酸変性ナノポリアクリルアミドゲルを形成し、冷却して使用に備える。
前記ステップ３は、前記ステップ２で得られたゲルに、前記ステップ１で調製したクエン酸鉄錯体を加え、６０℃に昇温し、高速で０．５ｈ撹拌し、鉄担持ゲルを得、得られた鉄担持ゲルを真空オーブンに置いて乾燥する。
前記ステップ４は、完全に乾燥したゲルをマッフル炉に置き、窒素気流中、１０℃／ｍｉｎの加熱速度で６００～９００℃で２ｈ炭化し、Ｆｅ＠Ｃ／Ｎナノハイブリッド、すなわち鉄基フィッシャー・トロプシュ合成触媒を得る。 A method for preparing an iron-based Fischer-Tropsch synthesis catalyst, which is prepared in steps 1 to 4.
In step 1, triiron tetroxide or iron oxide is dispersed in deionized water, citric acid is added, the temperature is raised to 80 ° C., and the mixture is stirred and cooled until the triiron tetroxide or iron oxide is completely dissolved. After filtering, insoluble impurities were filtered, and then aqueous ammonia was added to the filtrate to adjust the acid basicity, the pH was adjusted to 3 to 4, the temperature was raised to 85 ° C., and stirring was continued for 3 hours to obtain an iron citrate complex. Form and prepare for use.
In step 2, nanopolyacrylamide is dispersed in deionized water, amino acids are added, the temperature is raised to 90 ° C., and the mixture is stirred for 2 hours to form an amino acid-modified nanopolyacrylamide gel, which is cooled to prepare for use.
In step 3, the iron citrate complex prepared in step 1 is added to the gel obtained in step 2, the temperature is raised to 60 ° C., and the mixture is stirred at high speed for 0.5 h to obtain an iron-supported gel. Place the iron-supported gel in a vacuum oven to dry.
In step 4, the completely dried gel is placed in a muffle furnace, carbonized in a nitrogen stream at a heating rate of 10 ° C./min at 600 to 900 ° C. for 2 hours, and Fe @ C / N nanohybrid, that is, an iron-based Fischer. Obtain a Tropsch synthesis catalyst.

好ましくは、前記ステップ１における四酸化三鉄又は酸化鉄とクエン酸の配合比率は鉄元素とクエン酸のモル比が１：１．３‐１：１．４である。 Preferably, the compounding ratio of triiron tetroxide or iron oxide and citric acid in step 1 is a molar ratio of iron element to citric acid of 1: 1.3-1: 1.4.

好ましくは、前記ステップ２におけるナノポリアクリルアミドとアミノ酸との質量比は、１：０．１‐１：０．２であり、前記アミノ酸は、トリプトファンと、アラニンと、ロイシンとから選択される。 Preferably, the mass ratio of nanopolyacrylamide to the amino acid in step 2 is 1: 0.1-1: 0.2, and the amino acid is selected from tryptophan, alanine and leucine.

好ましくは、前記ステップ３におけるクエン酸鉄錯体とゲルとの質量比は、２‐３：７である。 Preferably, the mass ratio of the iron citrate complex to the gel in step 3 is 2-3: 7.

従来技術に比べ、本発明は下記のメリットを有する： The present invention has the following advantages over the prior art:

本発明のフィッシャー・トロプシュ合成触媒は、活性成分と担体とを含む。前記担体は、変性ゲルから調製され、クエン酸鉄を担持した後、高温焼成を経て触媒を形成する。担体中にＮ元素が含まれることにより、焼成中に鉄とＦｅ‐Ｎ‐Ｃ構造を形成することができ、鉄基触媒の触媒効率を効果的に向上させることができる。また、窒素原子が塩基性を有し、担体の表面塩基性が向上するとともに、担体の構造と活性成分とが結合し、目標生成物の選択性が高く、耐焼結性能に優れ、安定性の高いフィッシャー・トロプシュ合成触媒が得られる。 The Fischer-Tropsch synthesis catalyst of the present invention contains an active ingredient and a carrier. The carrier is prepared from a modified gel, carries iron citrate, and then undergoes high-temperature firing to form a catalyst. Since the N element is contained in the carrier, an Fe—NC structure can be formed with iron during firing, and the catalytic efficiency of the iron-based catalyst can be effectively improved. In addition, the nitrogen atom has basicity, the surface basicity of the carrier is improved, and the structure of the carrier and the active ingredient are bonded to each other, so that the target product has high selectivity, excellent sintering resistance, and stability. A high Fischer-Tropsch synthesis catalyst is obtained.

実施例１で調製された触媒が反応前の透過型電子顕微鏡写真である。The catalyst prepared in Example 1 is a transmission electron micrograph before the reaction. 実施例１で調製された触媒が８００ｈ反応した後の透過型電子顕微鏡写真である。It is a transmission electron micrograph after the catalyst prepared in Example 1 reacted for 800 hours.

以下に本発明における実施例を参照して、本発明における技術的解決手段を明確に、十分に説明する。 Hereinafter, the technical solutions in the present invention will be clearly and fully described with reference to the examples in the present invention.

実施例１
鉄基フィッシャー・トロプシュ合成触媒であって、ステップ１からステップ４で調製され、
前記ステップ１は、四酸化三鉄を脱イオン水に分散し、クエン酸を加え、８０℃に昇温して四酸化三鉄が完全に溶解するまで撹拌し、冷却して不溶性不純物を濾過し、濾過後、濾液にアンモニア水を加えて酸塩基性を調整し、ｐＨを３にした後、８５℃に昇温した後、３ｈ撹拌を続け、クエン酸鉄錯体を形成し、使用に備える。
前記ステップ２は、ナノポリアクリルアミドを脱イオン水に分散し、トリプトファンを加え、９０℃に昇温し、２ｈ撹拌し、変性ナノポリアクリルアミドゲルを形成し、冷却して使用に備える。
前記ステップ３は、前記ステップ２で得られたゲルに、前記ステップ１で調製したクエン酸鉄錯体を加え、６０℃に昇温し、高速で０．５ｈ撹拌し、鉄担持ゲルを得、得られた鉄担持ゲルを１２０℃の真空オーブンに置いて乾燥する。
前記ステップ４は、完全に乾燥したゲルをマッフル炉に置き、窒素気流中、１０℃／ｍｉｎの加熱速度で６００℃で２ｈ炭化し、Ｆｅ＠Ｃ／Ｎナノハイブリッド、すなわち鉄基フィッシャー・トロプシュ合成触媒を得る。
好ましくは、前記ステップ１における四酸化三鉄とクエン酸の配合比率は鉄元素とクエン酸のモル比が１：１．３である。
好ましくは、前記ステップ２におけるナノポリアクリルアミドとトリプトファンとの質量比は、１：０．１である。
好ましくは、前記ステップ３におけるクエン酸鉄錯体とゲルとの質量比は、２：７である。
本実施例で得られた鉄基フィッシャー・トロプシュ合成触媒１００ｍｇをフィッシャー・トロプシュ合成反応器に入れ、Ｈ２を２０ｍＬ／ｍｉｎの流量で注入し、４００℃で３ｈインサイチュ還元し、反応器の温度を３５０℃に下げた後、Ｈ２の注入を停止し、合成ガスの注入を開始し、前記合成ガスはＨ２とＣＯ体積比が１：１の混合気であり、３５０℃を維持し、圧力１ｂａｒ、合成ガス空間速度３０００ｍＬ／（ｈ・ｇ）の条件でフィッシャー・トロプシュ合成反応を行う。本実施例で得られた触媒の反応前及び８００ｈ反応後の透過型電子顕微鏡写真は、図１に示すように、触媒として８００ｈを使用したところ、触媒の表面には明確な炭素デポジットがない。 Example 1
An iron-based Fischer-Tropsch synthesis catalyst, prepared in steps 1 through 4.
In step 1, triiron tetroxide is dispersed in deionized water, citric acid is added, the temperature is raised to 80 ° C., stirring is performed until triiron tetroxide is completely dissolved, and the mixture is cooled to filter insoluble impurities. After filtration, aqueous ammonia is added to the filtrate to adjust the acid basicity, the pH is adjusted to 3, the temperature is raised to 85 ° C., and stirring is continued for 3 hours to form an iron citrate complex and prepare for use.
In step 2, nanopolyacrylamide is dispersed in deionized water, tryptophan is added, the temperature is raised to 90 ° C., and the mixture is stirred for 2 hours to form a modified nanopolyacrylamide gel, which is cooled to prepare for use.
In step 3, the iron citrate complex prepared in step 1 is added to the gel obtained in step 2, the temperature is raised to 60 ° C., and the mixture is stirred at high speed for 0.5 h to obtain an iron-supported gel. The iron-supported gel is placed in a vacuum oven at 120 ° C. and dried.
In step 4, the completely dried gel is placed in a muffle furnace, carbonized in a nitrogen stream at a heating rate of 10 ° C./min at 600 ° C. for 2 hours, and Fe @ C / N nanohybrid, that is, iron-based Fischer-Tropsch synthesis. Get a catalyst.
Preferably, the mixing ratio of triiron tetroxide and citric acid in step 1 is a molar ratio of element iron to citric acid of 1: 1.3.
Preferably, the mass ratio of nanopolyacrylamide to tryptophan in step 2 is 1: 0.1.
Preferably, the mass ratio of the iron citrate complex to the gel in step 3 is 2: 7.
100 mg of the iron-based Fischer-Tropsch synthesis catalyst obtained in this example was placed in a Fischer-Tropsch synthesis reactor, H2 was injected at a flow rate of 20 mL / min, and the temperature of the reactor was reduced by 3 hours at 400 ° C. After the temperature was lowered to 350 ° C., the injection of H 2 was stopped and the injection of the synthetic gas was started. The synthetic gas was a mixture of H 2 and a CO volume ratio of 1: 1 and maintained at 350 ° C., and the pressure was maintained. The Fischer-Tropsch synthesis reaction is carried out under the conditions of 1 bar and a syngas space velocity of 3000 mL / (h · g). In the transmission electron micrographs of the catalyst obtained in this example before and after the reaction for 800 hours, as shown in FIG. 1, when 800 h was used as the catalyst, there was no clear carbon deposit on the surface of the catalyst.

実施例２
鉄基フィッシャー・トロプシュ合成触媒であって、ステップ１からステップ４で調製され、
前記ステップ１は、四酸化三鉄を脱イオン水に分散し、クエン酸を加え、８０℃に昇温して四酸化三鉄が完全に溶解するまで撹拌し、冷却して不溶性不純物を濾過し、濾過後、濾液にアンモニア水を加えて酸塩基性を調整し、ｐＨを３．５にした後、８５℃に昇温した後、３ｈ撹拌を続け、クエン酸鉄錯体を形成し、使用に備える。
前記ステップ２は、ナノポリアクリルアミドを脱イオン水に分散し、アラニンを加え、９０℃に昇温し、２ｈ撹拌し、変性ナノポリアクリルアミドゲルを形成し、冷却して使用に備える。
前記ステップ３は、前記ステップ２で得られたゲルに、前記ステップ１で調製したクエン酸鉄錯体を加え、６０℃に昇温し、高速で０．５ｈ撹拌し、鉄担持ゲルを得、得られた鉄担持ゲルを１２０℃の真空オーブンに置いて乾燥する。
前記ステップ４は、完全に乾燥したゲルをマッフル炉に置き、窒素気流中、１０℃／ｍｉｎの加熱速度で７００℃で２ｈ炭化し、Ｆｅ＠Ｃ／Ｎナノハイブリッド、すなわち鉄基フィッシャー・トロプシュ合成触媒を得る。
好ましくは、前記ステップ１における四酸化三鉄とクエン酸の配合比率は鉄元素とクエン酸のモル比が１：１．３５である。
好ましくは、前記ステップ２におけるナノポリアクリルアミドとアラニンとの質量比は、１：０．１５である。
好ましくは、前記ステップ３におけるクエン酸鉄錯体とゲルとの質量比は、２．５：７である。 Example 2
An iron-based Fischer-Tropsch synthesis catalyst, prepared in steps 1 through 4.
In step 1, triiron tetroxide is dispersed in deionized water, citric acid is added, the temperature is raised to 80 ° C., stirring is performed until triiron tetroxide is completely dissolved, and the mixture is cooled to filter insoluble impurities. After filtration, add aqueous ammonia to the filtrate to adjust the acid basicity, adjust the pH to 3.5, raise the temperature to 85 ° C, and continue stirring for 3 hours to form an iron citrate complex for use. Be prepared.
In step 2, nanopolyacrylamide is dispersed in deionized water, alanine is added, the temperature is raised to 90 ° C., and the mixture is stirred for 2 hours to form a modified nanopolyacrylamide gel, which is cooled to prepare for use.
In step 3, the iron citrate complex prepared in step 1 is added to the gel obtained in step 2, the temperature is raised to 60 ° C., and the mixture is stirred at high speed for 0.5 h to obtain an iron-supported gel. The iron-supported gel is placed in a vacuum oven at 120 ° C. and dried.
In step 4, the completely dried gel is placed in a muffle furnace, carbonized at 700 ° C. at a heating rate of 10 ° C./min for 2 hours in a nitrogen stream, and Fe @ C / N nanohybrid, that is, iron-based Fischer-Tropsch synthesis. Get a catalyst.
Preferably, the compounding ratio of triiron tetroxide and citric acid in step 1 is a molar ratio of element iron to citric acid of 1: 1.35.
Preferably, the mass ratio of nanopolyacrylamide to alanine in step 2 is 1: 0.15.
Preferably, the mass ratio of the iron citrate complex to the gel in step 3 is 2.5: 7.

実施例３
鉄基フィッシャー・トロプシュ合成触媒であって、ステップ１からステップ４で調製され、
前記ステップ１は、酸化鉄を脱イオン水に分散し、クエン酸を加え、８０℃に昇温して四酸化三鉄が完全に溶解するまで撹拌し、冷却して不溶性不純物を濾過し、濾過後、濾液にアンモニア水を加えて酸塩基性を調整し、ｐＨを４にした後、８５℃に昇温した後、３ｈ撹拌を続け、クエン酸鉄錯体を形成し、使用に備える。
前記ステップ２は、ナノポリアクリルアミドを脱イオン水に分散し、ロイシンを加え、９０℃に昇温し、２ｈ撹拌し、変性ナノポリアクリルアミドゲルを形成し、冷却して使用に備える。
前記ステップ３は、前記ステップ２で得られたゲルに、前記ステップ１で調製したクエン酸鉄錯体を加え、６０℃に昇温し、高速で０．５ｈ撹拌し、鉄担持ゲルを得、得られた鉄担持ゲルを１２０℃の真空オーブンに置いて乾燥する。
前記ステップ４は、完全に乾燥したゲルをマッフル炉に置き、窒素気流中、１０℃／ｍｉｎの加熱速度で８００℃で２ｈ炭化し、Ｆｅ＠Ｃ／Ｎナノハイブリッド、すなわち鉄基フィッシャー・トロプシュ合成触媒を得る。
好ましくは、前記ステップ１における酸化鉄とクエン酸の配合比率は鉄元素とクエン酸のモル比が１：１．３である。
好ましくは、前記ステップ２におけるナノポリアクリルアミドとロイシンとの質量比は、１：０．２である。
好ましくは、前記ステップ３におけるクエン酸鉄錯体とゲルとの質量比は、２．５：７である。 Example 3
An iron-based Fischer-Tropsch synthesis catalyst, prepared in steps 1 through 4.
In step 1, iron oxide is dispersed in deionized water, citric acid is added, the temperature is raised to 80 ° C., stirring is performed until triiron tetroxide is completely dissolved, and the mixture is cooled to filter insoluble impurities and filtered. After that, aqueous ammonia was added to the filtrate to adjust the acid basicity, the pH was adjusted to 4, the temperature was raised to 85 ° C., and stirring was continued for 3 hours to form an iron citrate complex and prepare for use.
In step 2, nanopolyacrylamide is dispersed in deionized water, leucine is added, the temperature is raised to 90 ° C., and the mixture is stirred for 2 hours to form a modified nanopolyacrylamide gel, which is cooled to prepare for use.
In step 3, the iron citrate complex prepared in step 1 is added to the gel obtained in step 2, the temperature is raised to 60 ° C., and the mixture is stirred at high speed for 0.5 h to obtain an iron-supported gel. The iron-supported gel is placed in a vacuum oven at 120 ° C. and dried.
In step 4, the completely dried gel is placed in a muffle furnace, carbonized at 800 ° C. at a heating rate of 10 ° C./min for 2 hours in a nitrogen stream, and Fe @ C / N nanohybrid, that is, iron-based Fischer-Tropsch synthesis. Get a catalyst.
Preferably, the compounding ratio of iron oxide and citric acid in step 1 is a molar ratio of iron element to citric acid of 1: 1.3.
Preferably, the mass ratio of nanopolyacrylamide to leucine in step 2 is 1: 0.2.
Preferably, the mass ratio of the iron citrate complex to the gel in step 3 is 2.5: 7.

実施例４
鉄基フィッシャー・トロプシュ合成触媒であって、ステップ１からステップ４で調製され、
前記ステップ１は、四酸化三鉄を脱イオン水に分散し、クエン酸を加え、８０℃に昇温して四酸化三鉄が完全に溶解するまで撹拌し、冷却して不溶性不純物を濾過し、濾過後、濾液にアンモニア水を加えて酸塩基性を調整し、ｐＨを４にした後、８５℃に昇温した後、３ｈ撹拌を続け、クエン酸鉄錯体を形成し、使用に備える。
前記ステップ２は、ナノポリアクリルアミドを脱イオン水に分散し、ロイシンを加え、９０℃に昇温し、２ｈ撹拌し、変性ナノポリアクリルアミドゲルを形成し、冷却して使用に備える。
前記ステップ３は、前記ステップ２で得られたゲルに、前記ステップ１で調製したクエン酸鉄錯体を加え、６０℃に昇温し、高速で０．５ｈ撹拌し、鉄担持ゲルを得、得られた鉄担持ゲルを１２０℃の真空オーブンに置いて乾燥する。
前記ステップ４は、完全に乾燥したゲルをマッフル炉に置き、窒素気流中、１０℃／ｍｉｎの加熱速度で９００℃で２ｈ炭化し、Ｆｅ＠Ｃ／Ｎナノハイブリッド、すなわち鉄基フィッシャー・トロプシュ合成触媒を得る。
好ましくは、前記ステップ１における四酸化三鉄とクエン酸の配合比率は鉄元素とクエン酸のモル比が１：１．４である。
好ましくは、前記ステップ２におけるナノポリアクリルアミドとロイシンとの質量比は、１：０．２である。
好ましくは、前記ステップ３におけるクエン酸鉄錯体とゲルとの質量比は、３：７である。 Example 4
An iron-based Fischer-Tropsch synthesis catalyst, prepared in steps 1 through 4.
In step 1, triiron tetroxide is dispersed in deionized water, citric acid is added, the temperature is raised to 80 ° C., stirring is performed until triiron tetroxide is completely dissolved, and the mixture is cooled to filter insoluble impurities. After filtration, aqueous ammonia is added to the filtrate to adjust the acid basicity, the pH is adjusted to 4, the temperature is raised to 85 ° C., and stirring is continued for 3 hours to form an iron citrate complex and prepare for use.
In step 2, nanopolyacrylamide is dispersed in deionized water, leucine is added, the temperature is raised to 90 ° C., and the mixture is stirred for 2 hours to form a modified nanopolyacrylamide gel, which is cooled to prepare for use.
In step 3, the iron citrate complex prepared in step 1 is added to the gel obtained in step 2, the temperature is raised to 60 ° C., and the mixture is stirred at high speed for 0.5 h to obtain an iron-supported gel. The iron-supported gel is placed in a vacuum oven at 120 ° C. and dried.
In step 4, the completely dried gel is placed in a muffle furnace, carbonized at 900 ° C. at a heating rate of 10 ° C./min for 2 hours in a nitrogen stream, and Fe @ C / N nanohybrid, that is, iron-based Fischer-Tropsch synthesis. Get a catalyst.
Preferably, the mixing ratio of triiron tetroxide and citric acid in step 1 is 1: 1.4 in the molar ratio of element iron and citric acid.
Preferably, the mass ratio of nanopolyacrylamide to leucine in step 2 is 1: 0.2.
Preferably, the mass ratio of the iron citrate complex to the gel in step 3 is 3: 7.

比較例１
市販されている四酸化三鉄を触媒とする。（純度９９．５％、上海泰坦科技） Comparative Example 1
The catalyst is commercially available triiron tetroxide. (Purity 99.5%, Shanghai Taitan Technology)

比較例２
四酸化三鉄を脱イオン水に分散し、クエン酸を加え、８０℃に昇温して四酸化三鉄が完全に溶解するまで撹拌し、冷却して不溶性不純物を濾過し、濾過後、濾液にアンモニア水を加えて酸塩基性を調整し、ｐＨを３にした後、８５℃に昇温した後、３ｈ撹拌を続け、クエン酸鉄錯体を形成し、使用に備え、クエン酸鉄錯体の１２０℃の真空オーブンに放置して乾燥し、完全に乾燥したクエン酸鉄錯体をマッフル炉に置き、窒素気流中、１０℃／ｍｉｎの加熱速度で６００℃で２ｈ炭化し、鉄基フィッシャー・トロプシュ合成触媒を得る。 Comparative Example 2
Disperse triiron tetroxide in deionized water, add citric acid, heat to 80 ° C., stir until triiron tetroxide is completely dissolved, cool to filter insoluble impurities, filter and then filtrate. After adjusting the acid basicity by adding aqueous ammonia to adjust the pH to 3, the temperature was raised to 85 ° C., and then stirring was continued for 3 hours to form an iron citrate complex, and the iron citrate complex was prepared for use. It was left to dry in a vacuum oven at 120 ° C., and the completely dried iron citrate complex was placed in a muffle furnace and carbonized in a nitrogen stream at a heating rate of 10 ° C./min at 600 ° C. for 2 hours. Obtain a synthetic catalyst.

比較例３
特許ＣＮ１０２９１１６９４Ｂにおける実施例１の方法で調製された触媒。 Comparative Example 3
The catalyst prepared by the method of Example 1 in patent CN102911694B.

触媒性能試験
実施例１‐４、比較例１‐２で得られた触媒の触媒性能をそれぞれ試験したところ、試験結果を表１に示す。寿命とは、触媒の活性と選択性がほぼ変わらない場合に触媒を連続して使用できる時間を意味する。
上記触媒１０ｇを固定床反応器にとり反応させ、具体的な条件は、２１０℃、１．５Ｍｐａ、１０００ｈ‐１（Ｖ／Ｖ）、Ｈ２／ＣＯ（ｍｏｌ）＝２とした。
表１ 触媒性能試験結果

Figure 2022016242000002
表１から明らかなように、本発明により調製された触媒は、ＣＯ転化率がより高い、Ｃ５＋アルカン類選択性がより低く、メタン選択性がより低い。 Catalyst performance test The catalyst performance of the catalysts obtained in Example 1-4 and Comparative Example 1-2 was tested, and the test results are shown in Table 1. The lifetime means the time during which the catalyst can be used continuously when the activity and selectivity of the catalyst are not substantially different.
10 g of the above catalyst was reacted in a fixed bed reactor, and the specific conditions were 210 ° C., 1.5 Mpa, 1000 h -1 (V / V), H 2 / CO (mol) = 2.
Table 1 Catalyst performance test results
Figure 2022016242000002
As is clear from Table 1, the catalysts prepared by the present invention have higher CO conversion, lower C5 + alkanes selectivity, and lower methane selectivity.

Claims (5)

鉄基フィッシャー・トロプシュ合成触媒であって、
２０％～３０％の金属鉄と、残部の炭素とを含み、
前記炭素はナノポリアクリルアミド、クエン酸及びアミノ酸で調製される、
ことを特徴とする鉄基フィッシャー・トロプシュ合成触媒。 An iron-based Fischer-Tropsch synthesis catalyst
Contains 20% to 30% metallic iron and the balance of carbon
The carbon is prepared with nanopolyacrylamide, citric acid and amino acids.
An iron-based Fischer-Tropsch synthesis catalyst characterized by this. 前記鉄基フィッシャー・トロプシュ合成触媒の調製方法であって、ステップ１からステップ４で調製され、
前記ステップ１は、四酸化三鉄又は酸化鉄を脱イオン水に分散し、クエン酸を加え、８０℃に昇温して四酸化三鉄又は酸化鉄が完全に溶解するまで撹拌し、冷却して不溶性不純物を濾過し、濾過後、濾液にアンモニア水を加えて酸塩基性を調整し、ｐＨを３～４にし、そして８５℃に昇温した後、３ｈ撹拌を続け、クエン酸鉄錯体を形成し、
前記ステップ２は、ナノポリアクリルアミドを脱イオン水に分散し、アミノ酸を加え、９０℃に昇温し、２ｈ撹拌し、アミノ酸変性ナノポリアクリルアミドゲルを形成し、冷却して使用に備える。
前記ステップ３は、前記ステップ２で得られたゲルに、前記ステップ１で調製したクエン酸鉄錯体を加え、６０℃に昇温し、高速で０．５ｈ撹拌し、鉄担持ゲルを得、得られた鉄担持ゲルを真空オーブンに置いて乾燥し、
前記ステップ４は、完全に乾燥したゲルをマッフル炉に置き、窒素気流中、１０℃／ｍｉｎの加熱速度で６００～９００℃で２ｈ炭化し、Ｆｅ＠Ｃ／Ｎナノハイブリッド、すなわち鉄基フィッシャー・トロプシュ合成触媒を得る、
ことを特徴とする請求項１に記載の鉄基フィッシャー・トロプシュ合成触媒の調製方法。 The method for preparing an iron-based Fischer-Tropsch synthesis catalyst, which is prepared in steps 1 to 4.
In step 1, triiron tetroxide or iron oxide is dispersed in deionized water, citric acid is added, the temperature is raised to 80 ° C., and the mixture is stirred and cooled until the triiron tetroxide or iron oxide is completely dissolved. After filtering, insoluble impurities were filtered, and then aqueous ammonia was added to the filtrate to adjust the acid basicity, the pH was adjusted to 3 to 4, the temperature was raised to 85 ° C., and stirring was continued for 3 hours to obtain an iron citrate complex. Form and
In step 2, nanopolyacrylamide is dispersed in deionized water, amino acids are added, the temperature is raised to 90 ° C., and the mixture is stirred for 2 hours to form an amino acid-modified nanopolyacrylamide gel, which is cooled to prepare for use.
In step 3, the iron citrate complex prepared in step 1 is added to the gel obtained in step 2, the temperature is raised to 60 ° C., and the mixture is stirred at high speed for 0.5 h to obtain an iron-supported gel. Place the iron-supported gel in a vacuum oven to dry and
In step 4, the completely dried gel is placed in a muffle furnace, carbonized in a nitrogen stream at a heating rate of 10 ° C./min at 600 to 900 ° C. for 2 hours, and Fe @ C / N nanohybrid, that is, an iron-based Fischer. Obtain a Tropsch synthesis catalyst,
The method for preparing an iron-based Fischer-Tropsch synthesis catalyst according to claim 1. 前記ステップ１における四酸化三鉄又は酸化鉄とクエン酸の配合比率は鉄元素とクエン酸のモル比が１：１．３‐１：１．４である、
ことを特徴とする請求項２に記載の鉄基フィッシャー・トロプシュ合成触媒。 The compounding ratio of triiron tetroxide or iron oxide and citric acid in step 1 is such that the molar ratio of element iron to citric acid is 1: 1.3-1: 1.4.
The iron-based Fischer-Tropsch synthesis catalyst according to claim 2. 前記ステップ２におけるナノポリアクリルアミドとアミノ酸との質量比は、１：０．１‐１：０．２であり、前記アミノ酸は、トリプトファンと、アラニンと、ロイシンとから選択される、
ことを特徴とする請求項２に記載の鉄基フィッシャー・トロプシュ合成触媒。 The mass ratio of nanopolyacrylamide to the amino acid in step 2 is 1: 0.1-1: 0.2, and the amino acid is selected from tryptophan, alanine, and leucine.
The iron-based Fischer-Tropsch synthesis catalyst according to claim 2. 前記ステップ３におけるクエン酸鉄錯体とゲルとの質量比は、２‐３：７である、
ことを特徴とする請求項２に記載の鉄基フィッシャー・トロプシュ合成触媒。 The mass ratio of the iron citrate complex to the gel in step 3 is 2-3: 7.
The iron-based Fischer-Tropsch synthesis catalyst according to claim 2.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105195205A (en) * 2015-10-29 2015-12-30 江南大学 Preparation and application of N-doped Fe-based catalyst for Fischer-Tropsch reaction
CN108479834A (en) * 2018-03-19 2018-09-04 南京大学 A kind of fischer-tropsch synthetic catalyst and preparation method thereof
CN110773214A (en) * 2019-11-13 2020-02-11 广东工业大学 Carbon layer embedded iron carbide, preparation method thereof and application of carbon layer embedded iron carbide as Fischer-Tropsch synthesis catalyst

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105195205A (en) * 2015-10-29 2015-12-30 江南大学 Preparation and application of N-doped Fe-based catalyst for Fischer-Tropsch reaction
CN108479834A (en) * 2018-03-19 2018-09-04 南京大学 A kind of fischer-tropsch synthetic catalyst and preparation method thereof
CN110773214A (en) * 2019-11-13 2020-02-11 广东工业大学 Carbon layer embedded iron carbide, preparation method thereof and application of carbon layer embedded iron carbide as Fischer-Tropsch synthesis catalyst

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