JP2000254509A - Production of iron hydroxide type coal liquefying catalyst composition - Google Patents
Production of iron hydroxide type coal liquefying catalyst compositionInfo
- Publication number
- JP2000254509A JP2000254509A JP5869199A JP5869199A JP2000254509A JP 2000254509 A JP2000254509 A JP 2000254509A JP 5869199 A JP5869199 A JP 5869199A JP 5869199 A JP5869199 A JP 5869199A JP 2000254509 A JP2000254509 A JP 2000254509A
- Authority
- JP
- Japan
- Prior art keywords
- coal
- ammonia
- catalyst
- iron
- iron hydroxide
- 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.)
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Links
Abstract
Description
【０００１】[0001]
【発明が属する技術分野】本発明は、水酸化鉄系石炭液
化用触媒組成物及びその製造方法に関するものである。TECHNICAL FIELD The present invention relates to a catalyst composition for liquefying iron hydroxide-based coal and a method for producing the same.
【０００２】[0002]
【従来の技術】現在、世界のエネルギー資源の多くを石
油資源に頼っているが、この石油資源を有効に利用する
ため代替えエネルギーとして、褐炭、亜瀝青炭、瀝青炭
などの石炭液化技術の研究・開発が行われ、硫化鉄系及
び水酸化鉄系の触媒を使用し、内燃機関用（主として輸
送用の）燃料などに使用可能な付加価値の高い石炭液化
油が得られることは従来から知られている。2. Description of the Related Art At present, many of the world's energy resources are relied on petroleum resources, but research and development of coal liquefaction technologies, such as lignite, sub-bituminous coal, and bituminous coal, as alternative energies in order to make effective use of this petroleum resource. It has been known that high-value-added coal liquefied oil that can be used as fuel for internal combustion engines (mainly for transportation) can be obtained using iron sulfide-based and iron hydroxide-based catalysts. I have.
【０００３】石炭液化用触媒として開発が進められてい
る鉄−硫黄系触媒には、硫化鉄系及び水酸化鉄系の触媒
がある。前記水酸化鉄系触媒は、硫化鉄系触媒より触媒
能が高いが、量産技術が確立されていないため、石炭液
化の実用化試験には天然パイライト触媒及び合成硫化鉄
触媒が主として使用されてきた。[0003] Iron-sulfur catalysts which are being developed as coal liquefaction catalysts include iron sulfide catalysts and iron hydroxide catalysts. The iron hydroxide-based catalyst has a higher catalytic activity than the iron sulfide-based catalyst, but since mass production technology has not been established, a natural pyrite catalyst and a synthetic iron sulfide catalyst have been mainly used in a practical test of coal liquefaction. .
【０００４】[0004]
【発明が解決しようとする課題】ところで、天然パイラ
イト系硫化鉄触媒は、機械的に鉱石を粉砕することによ
り得られるが、天然パイライト鉱石は硬いため粉砕機や
液化プラント機器に著しい摩耗損傷を与えるという欠点
と、機械的粉砕のため、微硫化には限界があり触媒能に
限界があるという問題がある。The natural pyrite-based iron sulfide catalyst can be obtained by mechanically pulverizing ore. However, natural pyrite ore is hard and seriously damages the pulverizer and liquefaction plant equipment. However, there is a problem in that microsulfurization has a limit due to mechanical pulverization and catalytic ability has a limit.
【０００５】これに対して合成硫化鉄触媒は、合成とい
う特質から触媒粒子は天然パイライトより微粒とするこ
とができるので前記摩耗損傷を低減することができる。
しかしながら合成硫化鉄触媒は、液化触媒能に限界があ
り、所定の液化性能を得るためには使用料をある程度多
くせざるを得ないという欠点がある。[0005] On the other hand, the synthetic iron sulfide catalyst can reduce the abrasion damage because the catalyst particles can be finer than natural pyrite due to the characteristic of synthesis.
However, the synthetic iron sulfide catalyst has a drawback in that the liquefaction catalytic ability is limited, and in order to obtain a predetermined liquefaction performance, the usage fee must be increased to some extent.
【０００６】そこで最近では、水酸化鉄系の鉄化合物に
硫黄を添加して触媒とする方向に触媒開発が進んでい
る。ここで、水酸化鉄は、例えばリモナイト鉱のような
天然原料を使用する場合と、硫酸第一鉄−アンモニアか
ら合成する場合がある。前者は市場を通して原料調達が
未だ確立しておらず、後者は製造コストが高いというこ
とから、いずれも将来的な石炭液化用触媒として選定さ
れるには未だ課題を抱えている。Therefore, recently, catalyst development has been progressing in a direction of adding sulfur to an iron hydroxide-based iron compound to use it as a catalyst. Here, the iron hydroxide may be a case where a natural raw material such as limonite ore is used, or a case where it is synthesized from ferrous sulfate-ammonia. The former has not yet established raw material procurement through the market, and the latter has high production costs. Therefore, there are still problems in selecting them as future coal liquefaction catalysts.
【０００７】本発明者らは、液化プロセスにおいて容易
に得られるアンモニアを含む反応生成水の使用が可能な
アンモニア／鉄沈殿法（ＡＷＩＰ法）による鉄系高分散
触媒が工業的に有利である。即ち、ＡＷＩＰ法は、鉄−
硫黄系石炭液化触媒に属し、硫酸弱酸性溶液中で硫酸第
一鉄をアンモニア水と反応させ水酸化鉄を析出させるこ
とからなるものであり、原料である流硫酸第一鉄の鉄成
分及びアンモニア水は、石炭液化工程から得られる残渣
及び副生物として得ることができる。The present inventors have industrially advantageous an iron-based high-dispersion catalyst by an ammonia / iron precipitation method (AWIP method), which can use reaction water containing ammonia easily obtained in a liquefaction process. That is, the AWIP method uses iron-
It belongs to a sulfur-based coal liquefaction catalyst and consists of reacting ferrous sulfate with ammonia water in a weakly acidic sulfuric acid solution to precipitate iron hydroxide. Water can be obtained as residues and by-products from the coal liquefaction process.
【０００８】また前記反応を、石炭液化油などの溶剤に
分散された微粉炭の存在下に行わせ、微粉炭の表面に水
酸化鉄の微結晶を高度に分散させた状態で付着させた微
粉炭（触媒付着炭）を使用すると、石炭液化効率を向上
させることを確認している。しかもＡＷＩＰ法による前
記触媒は、従来型の合成硫化鉄触媒（以下ＳＩＳとい
う）の４分の１〜５分の１の触媒量でほぼ同等の液化性
能を示し、且つ褐炭、亜瀝青炭及び瀝青炭などの幅の広
い炭種に適用できるという各種の優れた特性を有してい
る。Further, the above reaction is carried out in the presence of pulverized coal dispersed in a solvent such as coal liquefied oil, and the fine powder of iron hydroxide is attached to the surface of the pulverized coal in a highly dispersed state. It has been confirmed that using coal (catalyst-attached coal) improves coal liquefaction efficiency. In addition, the catalyst prepared by the AWIP method exhibits almost the same liquefaction performance as a conventional synthetic iron sulfide catalyst (hereinafter referred to as SIS) at a catalyst amount of 1/4 to 1/5, and also includes lignite, subbituminous coal and bituminous coal. It has various excellent characteristics that it can be applied to a wide range of coal types.
【０００９】本発明は、ＡＷＩＰ法開発によって得た知
見に基づき完成させたものであり、性能のよい水酸化鉄
系石炭液化触媒組成物の製造方法を提供することを第一
の目的としている。The present invention has been completed based on the knowledge obtained by the development of the AWIP method, and has as its first object to provide a method for producing an iron hydroxide-based coal liquefaction catalyst composition having good performance.
【００１０】本発明の第二の目的は、水酸化鉄の原料で
ある硫酸第二鉄及びアンモニアを、石炭液化工程で循環
使用できる水酸化鉄系石炭液化触媒組成物の製造方法を
提供することにある。A second object of the present invention is to provide a method for producing an iron hydroxide-based coal liquefaction catalyst composition in which ferric sulfate and ammonia, which are raw materials of iron hydroxide, can be recycled in a coal liquefaction step. It is in.
【００１１】[0011]
【課題を解決するための手段】上記目的を達成するため
の本発明の水酸化鉄系石炭液化用触媒組成物の製造方法
は、硫酸酸性水溶液中で硫酸第一鉄を過酸化水素水によ
って酸化し、得られた硫酸第二鉄の酸性水溶液に硫酸ア
ンモニウムを添加して反応させ、反応生成物である水酸
化鉄及びアンモニアジャロサイト混合物を攪拌下に析出
させることからなるものである。In order to achieve the above object, the present invention provides a method for producing an iron hydroxide-based coal liquefaction catalyst composition, comprising the steps of oxidizing ferrous sulfate with a hydrogen peroxide solution in a sulfuric acid aqueous solution. Then, ammonium sulfate is added to the obtained acidic aqueous solution of ferric sulfate to cause a reaction, and a mixture of iron hydroxide and ammonia jarosite, which is a reaction product, is precipitated under stirring.
【００１２】前記水酸化鉄及びアンモニアジャロサイト
混合物の析出は、攪拌下に常温に保持（以下熟成とい
う）することが好ましい。熟成温度を上げるとアンモニ
アジャロサイトの結晶の成長が速くなり触媒能が低下す
ることが認められる。したがって、Ｘ線回折パターンな
どにより、アンモニアジャロサイトの結晶の存在が僅か
に認められるようになった段階で熟成を終了させること
が好ましい。前記硫酸酸性の酸度は、弱酸性とする。ｐ
Ｈ値としては、２〜３、好ましくは２〜２．５の範囲に
保持することが好ましい。The precipitation of the mixture of iron hydroxide and ammonia jarosite is preferably maintained at room temperature with stirring (hereinafter referred to as aging). It is recognized that when the aging temperature is increased, the growth of ammonia jarosite crystals is accelerated and the catalytic ability is reduced. Therefore, it is preferable to terminate the ripening when the presence of ammonia jarosite crystals is slightly recognized by the X-ray diffraction pattern or the like. The acidity of the sulfuric acid is weakly acidic. p
The H value is preferably kept in the range of 2 to 3, preferably 2 to 2.5.
【００１３】前記酸化反応の各原料は、順次添加しても
よく、また同時に添加してもよい。また、前記水酸化鉄
−アンモニアジャロサイト沈殿物の回収方法は、特に限
定はなく、例えばろ過、加圧脱水などの手段を用いるこ
とができる。The raw materials for the oxidation reaction may be added sequentially or simultaneously. The method for collecting the iron hydroxide-ammonia jarosite precipitate is not particularly limited, and for example, means such as filtration and dehydration under pressure can be used.
【００１４】被液化用微粉炭上に、水酸化鉄微粉及びア
ンモニアジャロサイトの混合物を、高度に分散させた状
態で付着（析出）させて触媒付着炭とし、この触媒付着
炭を微粉炭スラリーに混入して使用することが好まし
い。On a pulverized coal for liquefaction, a mixture of iron hydroxide fine powder and ammonia jarosite is deposited (precipitated) in a highly dispersed state to form a catalyst-coated carbon, and the catalyst-coated carbon is converted into a pulverized coal slurry. It is preferable to mix them.
【００１５】前記硫酸第一鉄原料としては、特に限定は
ないが、微粉炭を鉄−硫黄系の石炭液化触媒の存在下に
微粉炭を水素と反応させ、得られた石炭液化油の蒸留残
渣から鉄を回収し、硫酸第一鉄原料として循環使用する
ことが有利である。The ferrous sulfate raw material is not particularly limited, but pulverized coal is reacted with hydrogen in the presence of an iron-sulfur-based coal liquefaction catalyst, and the distillation residue of the obtained coal liquefied oil is obtained. It is advantageous to recover the iron from the iron and recycle it as a ferrous sulfate raw material.
【００１６】また、硫酸アンモニウムのアンモニウム原
料として、微粉炭を鉄−硫黄系の石炭液化触媒の存在下
に微粉炭を水素と反応させる石炭液化工程又は石炭液化
油の蒸留工程で得られるアンモニア含有排水を循環使用
することが有利である。Further, as an ammonium raw material for ammonium sulfate, ammonia-containing wastewater obtained in a coal liquefaction step in which pulverized coal is reacted with hydrogen in the presence of an iron-sulfur coal liquefaction catalyst or a coal liquefied oil distillation step is used. It is advantageous to use it cyclically.
【００１７】以上説明した水酸化鉄系石炭液化用触媒組
成物の製造方法は、アンモニアジャロサイトを合成する
条件の下で、水酸化鉄を合成するように原料を調製し、
得られた沈殿物を含む溶液を、アンモニアジャロサイト
結晶が僅かに認められる程度となった段階で熟成を終了
させ、析出したγ−水酸化鉄及びアンモニアジャロサイ
トの混合沈殿物を回収することが、触媒能を向上させる
点で好ましい。In the method for producing the iron hydroxide-based coal liquefaction catalyst composition described above, a raw material is prepared so as to synthesize iron hydroxide under conditions for synthesizing ammonia jarosite.
The solution containing the obtained precipitate is subjected to aging at a stage where ammonia jarosite crystals are slightly recognized, and a mixed precipitate of precipitated γ-iron hydroxide and ammonia jarosite can be recovered. This is preferable in that it improves the catalytic ability.
【００１８】前記熟成を終了時点は、反応液をサンプリ
ングし、Ｘ線回折（ＸＲＤ）によりアンモニアジャロサ
イト結晶が僅かに確認された時点を熟成終了とすること
が好ましい。Preferably, the ripening is terminated when the reaction liquid is sampled and the ammonia jarosite crystals are slightly confirmed by X-ray diffraction (XRD).
【００１９】以上、アンモニアジャロサイトの晶析反応
条件及びその後の熟成条件によって、アンモニアジャロ
サイト結晶の含有量及び結晶粒径が異なるが、それに伴
い沈殿する水酸化鉄（詳しくはγ−水酸化鉄）の含有
量、粒径も異なるようになる。最適条件で沈殿物を回収
すると、極めて微細な粒子径のγ−水酸化鉄を約７０mo
l%含有させることができ、アンモニアジャロサイトの結
晶粒径は約１μｍである。As described above, the content of ammonia jarosite crystals and the crystal grain size vary depending on the crystallization reaction conditions of ammonia jarosite and the subsequent aging conditions. )) And the particle size also differ. When the precipitate is recovered under the optimal conditions, γ-iron hydroxide having an extremely fine particle diameter is reduced to about 70 mol.
l%, and the crystal grain size of ammonia jarosite is about 1 μm.
【００２０】[0020]
【発明の実施の形態】以下添付の図を参照して一実施の
形態により本発明を具体的に説明する。図１によって、
本実施の形態による水酸化鉄系石炭液化用触媒組成物の
製造方法に使用した装置について説明する。図におい
て、広口フラスコからなる反応容器１をホットプレート
スターラー２に乗せ、内部に温度計３を取り付ける。反
応容器１の傍らに置いたビーカー４内の過酸化水素水５
は、ベリスタポンプ６によって反応容器１内に送入でき
るようにした。なお図１に示す符号７は、前記ホットプ
レートスターラー２内には回転磁界発生装置（図示せ
ず）によって回転する鉄片封入の攪拌翼、８は電源コー
ドである。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below with reference to an embodiment shown in the accompanying drawings. According to FIG.
An apparatus used in the method for producing the iron hydroxide-based coal liquefaction catalyst composition according to the present embodiment will be described. In the figure, a reaction vessel 1 composed of a wide-necked flask is placed on a hot plate stirrer 2 and a thermometer 3 is mounted inside. Hydrogen peroxide solution 5 in beaker 4 placed beside reaction vessel 1
Can be fed into the reaction vessel 1 by the verista pump 6. Reference numeral 7 shown in FIG. 1 denotes an agitating blade enclosed in an iron piece which is rotated by a rotating magnetic field generator (not shown) in the hot plate stirrer 2, and 8 denotes a power cord.
【００２１】以上説明した反応装置を使用した実施例を
以下に説明する。 〔実施例１〕実施例１に使用した各反応原料組成を表１
に示す。An embodiment using the above-described reactor will be described below. [Example 1] Table 1 shows the composition of each reaction raw material used in Example 1.
Shown in
【００２２】[0022]
【表１】 [Table 1]
【００２３】先ず、反応容器１に粉末状の硫酸第一鉄９
と硫酸水溶液（希硫酸）10とを入れ、よく攪拌しながら
昇温速度５℃／分で４０℃まで昇温させながら硫酸第一
鉄を溶解させ、前記温度を保ちながら過酸化水素水５を
ベリスタポンプ６によって０．７ml／分の速度で反応容
器１内に滴下し、硫酸第一鉄を硫酸第二鉄に酸化し、全
量（１００ml）を滴下した後、硫酸アンモニウム11を反
応容器１内に添加し、添加後１〜２分程度攪拌を継続
し、温度を常温まで放冷などの手段により冷却する。First, powdered ferrous sulfate 9 is placed in a reaction vessel 1.
And sulfuric acid aqueous solution (dilute sulfuric acid) 10, ferrous sulfate is dissolved while increasing the temperature to 40 ° C. at a rate of 5 ° C./min with good stirring, and hydrogen peroxide solution 5 is added while maintaining the above temperature. The ferrite sulfate was oxidized into ferric sulfate at a rate of 0.7 ml / min by the vesting pump 6 at a rate of 0.7 ml / min, and the entire amount (100 ml) was dropped. After the addition, stirring is continued for about 1 to 2 minutes after the addition, and the temperature is cooled to room temperature by cooling or the like.
【００２４】硫酸アンモニウム11の添加が終わった段階
では、アンモニアジャロサイトの結晶析出は起こらず、
常温で攪拌を継続しながら溶液を熟成させる。このと
き、溶液のｐＨは２〜３、好ましくは２〜２．５に保持
することが必要である。熟成期間中は、恒温状態で、酸
化を防ぐため空気を遮断することが好ましいが、本発明
は必ずしもこれに限定されない。At the stage when the addition of ammonium sulfate 11 has been completed, no crystallization of ammonia jarosite occurs,
The solution is aged while stirring at room temperature. At this time, it is necessary to maintain the pH of the solution at 2-3, preferably 2-2.5. During the aging period, it is preferable to shut off the air at a constant temperature to prevent oxidation, but the present invention is not necessarily limited to this.
【００２５】熟成をいつまで継続するかの判断は、熟成
中の触媒をサンプリングし、ＸＲＤにより、ジャイロサ
イト結晶のパターンの存在が僅かでも確認されたとき、
熟成を終了させるのが実際的である。溶液が５０℃以上
の温度に加熱すると短時間でジャロサイトの結晶が析出
し、粒径が大きくなり、触媒能が低下するので好ましく
ない。析出物は真空濾過により回収した。以上によって
得た合成物中にアンモニアジャロサイト結晶及びγ−水
酸化鉄が存在することを、電子顕微鏡、ＸＲＤ及びメス
バウアー分光分析により確認した。The determination of how long the ripening should be continued is made by sampling the catalyst during the ripening and, when XRD confirms the presence of any gyrosite crystal pattern,
It is practical to end the ripening. When the solution is heated to a temperature of 50 ° C. or higher, jarosite crystals are precipitated in a short time, the particle size becomes large, and the catalytic activity is undesirably reduced. The precipitate was collected by vacuum filtration. The presence of ammonia jarosite crystals and γ-iron hydroxide in the synthesized product was confirmed by an electron microscope, XRD and Mossbauer spectroscopy.
【００２６】前記熟成期間を種々変更（一部攪拌速度を
変更）してアンモニアジャロサイト結晶を析出させＸＲ
Ｄ回折を行ったところ、図２に示すとおり、熟成を１０
日以上、特に２０日以上行ったものはアンモニアジャロ
サイトの結晶が成長していることが認められた。なお、
図２においてｊｈ−０１などの記号は試料番号である。The aging period was variously changed (partially the stirring speed was changed) to precipitate ammonia jarosite crystals, and the XR
When D diffraction was carried out, as shown in FIG.
It was confirmed that the crystals of ammonia jarosite grew when the test was performed for more than 20 days, especially for more than 20 days. In addition,
In FIG. 2, symbols such as jh-01 are sample numbers.
【００２７】〔実施例２〕実施例１の硫酸第二鉄を生成
させた段階で、微粉炭（１００メッシュ全通）２５ｇを
添加した外は、実施例１と同様にして水酸化鉄系石炭液
化用触媒組成物を合成し、前記ＸＲＤ回折と同時に、電
子顕微鏡、メスバウアー分光分析によりジャロサイト結
晶及びγ−水酸化鉄の存在を確認した。Example 2 Iron hydroxide-based coal was prepared in the same manner as in Example 1 except that 25 g of pulverized coal (100 mesh whole) was added at the stage of producing ferric sulfate of Example 1. A catalyst composition for liquefaction was synthesized, and the presence of jarosite crystals and γ-iron hydroxide were confirmed by electron microscopy and Mossbauer spectroscopy simultaneously with the XRD diffraction.
【００２８】また、熟成期間をパラメータとして触媒添
加量と（水＋オイル）収率との関係を求めたところ、図
３に示すとおり、アンモニアジャロサイトの結晶成長が
認められるかどうかのところで熟成を停止させたもの
は、ＡＷＩＰ触媒と同等かそれに近い液化性能を示す結
果を得た。特に、熟成期間が２日のものは、触媒添加量
が多い領域でＡＷＩＰ触媒を凌ぐ液化収率を示してお
り、本発明触媒組成物製造方法の目的が達成されたこと
を確認することができた。When the relationship between the amount of catalyst added and the (water + oil) yield was determined using the aging period as a parameter, as shown in FIG. 3, the aging was performed in the presence of crystal growth of ammonia jarosite. In the case where the AWIP catalyst was stopped, a result showing liquefaction performance equivalent to or close to that of the AWIP catalyst was obtained. In particular, when the aging period is 2 days, the liquefaction yield is higher than that of the AWIP catalyst in the region where the amount of added catalyst is large, and it can be confirmed that the object of the catalyst composition production method of the present invention has been achieved. Was.
【００２９】[0029]
【発明の効果】以上説明したとおり本発明の水酸化鉄系
石炭液化用触媒組成物は、石炭液化用鉄−硫黄系触媒と
して触媒能の高い水酸化鉄の合成をアンモニアジャロサ
イト合成条件で行い、望ましくはアンモニアジャロサイ
ト結晶析出状態を指標として熟成を終了させた触媒を使
用することにより、高い収率で石炭液化油を得ることが
できるという効果が得られる。特に最適条件の下では、
ＡＷＩＰ法を凌ぐ液化収率を得ることができる。As described above, the iron hydroxide-based coal liquefaction catalyst composition of the present invention can be used as an iron-sulfur-based catalyst for coal liquefaction by synthesizing iron hydroxide having a high catalytic activity under ammonia jarosite synthesis conditions. Preferably, the use of a catalyst whose aging has been completed using the ammonia jarosite crystal precipitation state as an index provides an effect that a coal liquefied oil can be obtained with a high yield. Especially under optimal conditions,
A liquefaction yield exceeding the AWIP method can be obtained.
【００３０】また、本発明方法において使用する原料の
うち、第一硫酸鉄、硫酸アンモニウム水の原料の大部分
は石炭液化工程の副生物及び残渣から得ることができ、
また酸化剤である過酸化水素水は残渣成分を全く含まな
いため、廃棄物を可及的に低減させることができるとい
う効果を奏することができる。Further, among the raw materials used in the method of the present invention, most of the raw materials of ferrous sulfate and ammonium sulfate can be obtained from by-products and residues of the coal liquefaction step,
In addition, since the hydrogen peroxide solution as the oxidizing agent does not contain any residual components, it is possible to achieve an effect that waste can be reduced as much as possible.
【図１】本発明の水酸化鉄系石炭液化用触媒組成物の製
造方法の概要を説明するための実験室規模装置の斜視図
である。FIG. 1 is a perspective view of a laboratory-scale apparatus for explaining the outline of the method for producing the iron hydroxide-based coal liquefaction catalyst composition of the present invention.
【図２】本発明の実施例１において、アンモニアジャロ
サイト結晶を熟成期間を変えて析出させて得た各種の水
酸化鉄系石炭液化用触媒組成物を用いて触媒添加量と
（水＋液化油）収率との関係を示したグラフ図である。FIG. 2 shows the amounts of catalyst added and (water + liquefaction) using various iron hydroxide-based coal liquefaction catalyst compositions obtained by depositing ammonia jarosite crystals with different aging periods in Example 1 of the present invention. FIG. 4 is a graph showing a relationship with oil (yield).
【図３】本発明の実施例２において、アンモニアジャロ
サイト結晶のＸ線回折角と回折強度との関係を熟成期間
を変えて測定した結果を示すグラフ図である。FIG. 3 is a graph showing the results of measuring the relationship between the X-ray diffraction angle and the diffraction intensity of ammonia jarosite crystals in Example 2 of the present invention while changing the aging period.
１ 反応容器 ５ 過酸化水素水 ９ 硫酸第一鉄 10 硫酸水溶液 11 硫酸アンモニウム 1 Reaction vessel 5 Hydrogen peroxide solution 9 Ferrous sulfate 10 Sulfuric acid aqueous solution 11 Ammonium sulfate
───────────────────────────────────────────────────── フロントページの続き (72)発明者 濱中 義孝 千葉県市原市八幡海岸通１番地 三井造船 株式会社千葉事業所内 Ｆターム(参考） 4G002 AA12 AB02 AB05 AE05 4G069 AA03 AA08 BA08A BA08B BA08C BB10A BB10B BB10C BC66A BC66B BC66C BD08A BD08B BD08C BE17A BE17B BE17C CC20 DA08 EA01X EA01Y FB05 FB06 FB08 FC02 4H029 CA00 DA00 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yoshitaka Hamanaka 1st floor of Yawata Kaigan, Ichihara-shi, Chiba Mitsui Engineering & Shipbuilding Co., Ltd. Chiba Works F-term (reference) 4G002 AA12 AB02 AB05 AE05 4G069 AA03 AA08 BA08A BA08B BA08C BB10A BB10B BB10C BC66A BC66B BC66C BD08A BD08B BD08C BE17A BE17B BE17C CC20 DA08 EA01X EA01Y FB05 FB06 FB08 FC02 4H029 CA00 DA00
Claims (5)
水素水によって酸化し、得られた硫酸第二鉄の酸性水溶
液に硫酸アンモニウムを添加して反応させ、反応生成物
である水酸化鉄及びアンモニアジャロサイト混合物を攪
拌下に析出させることからなる請求項１記載の水酸化鉄
系石炭液化用触媒組成物の製造方法。1. A ferrous sulfate is oxidized with an aqueous solution of hydrogen peroxide in an aqueous sulfuric acid solution, and ammonium sulfate is added to the obtained acidic aqueous solution of ferric sulfate to cause a reaction. The method for producing a catalyst composition for iron hydroxide-based coal liquefaction according to claim 1, further comprising precipitating the ammonia and jarosite mixture under stirring.
ト混合物の析出を、アンモニアジャロサイトの結晶の存
在が僅かに認められた段階で終了させることからなる請
求項１記載の石炭液化触媒の製造方法。2. The method for producing a coal liquefaction catalyst according to claim 1, wherein the precipitation of the mixture of iron hydroxide and ammonia jarosite is terminated when the presence of ammonia jarosite crystals is slightly recognized.
粉炭を水素と反応させ、得られた石炭液化油の蒸留残渣
から鉄を回収し、硫酸第一鉄原料として循環使用するこ
とからなる請求項１又は２記載の水酸化鉄系石炭液化用
触媒組成物の製造方法。3. Reacting pulverized coal with hydrogen in the presence of an iron-sulfur coal liquefaction catalyst, recovering iron from the distillation residue of the obtained coal liquefied oil, and circulating it as a ferrous sulfate raw material. The method for producing a catalyst composition for liquefying iron hydroxide-based coal according to claim 1 or 2, comprising:
粉炭を水素とを反応させ、液化反応工程又は石炭液化油
の蒸留工程で得られるアンモニア含有排水を前記硫酸ア
ンモニウムのアンモニア原料として循環使用することか
らなる請求項１、２又は３記載の水酸化鉄系石炭液化用
触媒組成物の製造方法。石炭液化触媒の製造方法。4. A pulverized coal is reacted with hydrogen in the presence of an iron-sulfur coal liquefaction catalyst, and ammonia-containing wastewater obtained in a liquefaction reaction step or a coal liquefaction oil distillation step is circulated as the ammonia raw material for the ammonium sulfate. The method for producing a catalyst composition for liquefying iron hydroxide-based coal according to claim 1, wherein the catalyst composition is used. A method for producing a coal liquefaction catalyst.
化する際に、被液化用微粉炭を分散させた反応液中で酸
化させることからなる請求項１、２、３又は４記載の水
酸化鉄系石炭液化用触媒組成物の製造方法。5. The water according to claim 1, wherein the ferrous sulfate is oxidized with hydrogen peroxide in a reaction solution in which pulverized coal for liquefaction is dispersed. A method for producing an iron oxide-based coal liquefaction catalyst composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5869199A JP2000254509A (en) | 1999-03-05 | 1999-03-05 | Production of iron hydroxide type coal liquefying catalyst composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5869199A JP2000254509A (en) | 1999-03-05 | 1999-03-05 | Production of iron hydroxide type coal liquefying catalyst composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000254509A true JP2000254509A (en) | 2000-09-19 |
Family
ID=13091584
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|---|---|---|---|
| JP5869199A Withdrawn JP2000254509A (en) | 1999-03-05 | 1999-03-05 | Production of iron hydroxide type coal liquefying catalyst composition |
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| Country | Link |
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| JP (1) | JP2000254509A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002018287A (en) * | 2000-07-06 | 2002-01-22 | Mitsui Eng & Shipbuild Co Ltd | Iron hydroxide type coal liquefying catalyst composition and method for manufacturing the same |
| WO2004069405A1 (en) * | 2003-02-03 | 2004-08-19 | Mitsui Engineering & Shipbuilding Co., Ltd. | Method for preparing highly active catalyst for coal liquefaction |
| JP2006175434A (en) * | 2004-12-23 | 2006-07-06 | Sud-Chemie Catalysts Italia Srl | Production method for catalyst for oxidation of methanol to formaldehyde |
| CN104549277A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Residual oil catalyst and preparation method and application of residual oil catalyst |
| CN110257117A (en) * | 2019-07-10 | 2019-09-20 | 中国神华煤制油化工有限公司 | A kind of liquefied coal coil coal slurry preparation method of supported catalyst |
| JP2020199469A (en) * | 2019-06-12 | 2020-12-17 | 独立行政法人国立高等専門学校機構 | Oxidation-promoting catalyst and method for producing the same |
-
1999
- 1999-03-05 JP JP5869199A patent/JP2000254509A/en not_active Withdrawn
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002018287A (en) * | 2000-07-06 | 2002-01-22 | Mitsui Eng & Shipbuild Co Ltd | Iron hydroxide type coal liquefying catalyst composition and method for manufacturing the same |
| WO2004069405A1 (en) * | 2003-02-03 | 2004-08-19 | Mitsui Engineering & Shipbuilding Co., Ltd. | Method for preparing highly active catalyst for coal liquefaction |
| CN100361743C (en) * | 2003-02-03 | 2008-01-16 | 三井造船株式会社 | Method for preparing highly active catalyst for coal liquefaction |
| JP2006175434A (en) * | 2004-12-23 | 2006-07-06 | Sud-Chemie Catalysts Italia Srl | Production method for catalyst for oxidation of methanol to formaldehyde |
| CN104549277A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Residual oil catalyst and preparation method and application of residual oil catalyst |
| JP2020199469A (en) * | 2019-06-12 | 2020-12-17 | 独立行政法人国立高等専門学校機構 | Oxidation-promoting catalyst and method for producing the same |
| CN110257117A (en) * | 2019-07-10 | 2019-09-20 | 中国神华煤制油化工有限公司 | A kind of liquefied coal coil coal slurry preparation method of supported catalyst |
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