JPH10310426A - Production of pseudoboehmite alumina and production of hydrodesulfurization catalyst carrier using the alumina - Google Patents
Production of pseudoboehmite alumina and production of hydrodesulfurization catalyst carrier using the aluminaInfo
- Publication number
- JPH10310426A JPH10310426A JP9124702A JP12470297A JPH10310426A JP H10310426 A JPH10310426 A JP H10310426A JP 9124702 A JP9124702 A JP 9124702A JP 12470297 A JP12470297 A JP 12470297A JP H10310426 A JPH10310426 A JP H10310426A
- Authority
- JP
- Japan
- Prior art keywords
- alumina
- sulfuric acid
- catalyst
- water
- washing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、硫黄化合物及び窒
素化合物を含有する炭化水素油の水素化脱硫触媒の製造
方法に関わり、特に、水素化脱硫触媒の原料である擬ベ
ーマイトアルミナ及びその擬ベーマイトアルミナを用い
て製造する水素化脱硫触媒の担体に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a hydrodesulfurization catalyst for a hydrocarbon oil containing a sulfur compound and a nitrogen compound, and more particularly to pseudo-boehmite alumina and pseudo-boehmite as raw materials for the hydrodesulfurization catalyst. The present invention relates to a support for a hydrodesulfurization catalyst produced using alumina.
【０００２】[0002]
【従来の技術】一般に原油或いは原油から軽質留分を分
離した残渣油は、硫黄含有濃度が高いため、脱硫処理し
た後、次工程で処理されたり、燃料として利用される。
残渣油等に含まれる硫黄化合物を除去するには、一般に
アルミナ或いはシリカアルミナを担体として、これに活
性金属を担持させた水素化脱硫触媒を用い、水素加圧下
で加熱処理する方法が用いられている。また、この脱硫
処理工程では、硫黄が硫化水素となり除去される反応と
同時に、窒素化合物がアンモニアとして除去される。2. Description of the Related Art In general, crude oil or residual oil obtained by separating light fractions from crude oil has a high sulfur content, so that it is desulfurized and then processed in the next step or used as fuel.
In order to remove sulfur compounds contained in residual oils and the like, a method of performing heat treatment under hydrogen pressure using a hydrodesulfurization catalyst having alumina or silica alumina as a carrier and an active metal supported thereon is generally used. I have. In this desulfurization treatment step, the nitrogen compound is removed as ammonia at the same time as the reaction in which sulfur is converted to hydrogen sulfide and removed.
【０００３】従来、このような触媒には、脱硫活性が高
いこと、寿命が長いこと、安価であることが求められて
おり、これらに重点を置いた検討がなされてきた。そし
て、脱硫性能という点では、ほぼ十分な性能を有するも
のが使われるようになった。しかし、近年、大気汚染物
質の規制が強化されるに従い、窒素酸化物の排出抑制が
求められるようになってきた。このため、脱硫触媒には
脱硫性能もさることながら、脱窒素活性に優れるものが
求められるようになった。脱窒素活性を高めるために
は、触媒活性金属の担持量を増やす方法が考えられる。
しかし、触媒活性金属の増量は触媒価格の向上につなが
る。Conventionally, such a catalyst has been required to have a high desulfurization activity, a long life, and to be inexpensive, and studies have been made with emphasis on these. In terms of desulfurization performance, those having almost sufficient performance have come to be used. However, in recent years, as regulations on air pollutants have been tightened, it has been required to reduce the emission of nitrogen oxides. For this reason, a desulfurization catalyst that has excellent desulfurization activity as well as desulfurization performance has been required. In order to increase the denitrification activity, a method of increasing the amount of the catalytically active metal carried can be considered.
However, increasing the amount of catalytically active metal leads to an increase in catalyst price.
【０００４】一方、脱硫触媒に用いられるアルミナ原料
は、アルミニウム塩の中和法や、アルミニウムアルコキ
シドを加水分解するアルホール法によって得られる擬ベ
ーマイトアルミナが主に用いられている。このような擬
ベーマイトアルミナは、触媒の被毒成分であるアルカリ
金属や、触媒活性に影響の大きい硫酸や塩酸等の鉱酸を
除去したものを用いるのが一般的である。しかし、特公
昭５０−１２３９７号広報には、安定性に優れた触媒を
得るため、硫酸根を含有するアルミナ原料を用い、これ
を６００〜１１００℃で焼成して硫酸根を０．５〜５質
量％含有するアルミナ担体を製造し、脱硫触媒とするこ
とが記載されている。しかしながら、硫酸根を担持し、
しかもこのような高温で焼成して得られる担体に活性成
分を担持した触媒は、活性が著しく低下することが多
い。On the other hand, as an alumina raw material used for a desulfurization catalyst, pseudo-boehmite alumina obtained by a neutralization method of an aluminum salt or an Alhol method of hydrolyzing an aluminum alkoxide is mainly used. Such pseudo-boehmite alumina is generally used after removing alkali metals, which are poison components of the catalyst, and mineral acids, such as sulfuric acid and hydrochloric acid, which greatly affect the catalytic activity. However, Japanese Patent Publication No. 50-12397 discloses that in order to obtain a catalyst having excellent stability, an alumina raw material containing a sulfate group is used, which is calcined at 600 to 1100 ° C. to reduce the sulfate group to 0.5 to 5%. It describes that an alumina carrier containing a mass% is produced and used as a desulfurization catalyst. However, they carry sulfate groups,
In addition, the activity of a catalyst obtained by calcining at such a high temperature and carrying an active ingredient on a carrier often significantly decreases.
【０００５】[0005]
【発明が解決しようとする課題】本発明の課題は、触媒
活性金属量を増やすことなく、脱窒素活性に優れる脱硫
触媒の製造を可能にする擬ベーマイトアルミナの製造方
法と、その擬ベーマイトアルミナを用いる脱硫触媒用担
体の製造方法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing pseudo-boehmite alumina which enables production of a desulfurization catalyst having excellent denitrification activity without increasing the amount of catalytically active metal, and a method for producing pseudo-boehmite alumina. An object of the present invention is to provide a method for producing a carrier for a desulfurization catalyst to be used.
【０００６】[0006]
【課題を解決するための手段】本発明者が、アルミナ原
料に注目し、鋭意検討を進めた結果、硫酸を含有する洗
浄水で洗浄した擬ベーマイトアルミナを成形し、４５０
〜６５０℃で焼成した担体を用いて触媒を製造すると、
脱窒素活性を大幅に向上できることを見出した。しかも
脱硫活性は、硫酸分を含有しない擬ベーマイトアルミナ
原料を用いた触媒と同等であった。さらに、上記擬ベー
マイトアルミナの製造条件を検討した結果、ｐＨ８．０
〜９．５で製造した水酸化アルミニウムを濾別し、得ら
れる水酸化アルミニウムケーキを硫酸及び／又は硫酸ア
ンモニウム添加水で洗浄する際に、濾液のｐＨが８．０
±０．５となるように管理して洗浄し乾燥する方法と、
濾別した前記水酸化アルミニウムケーキを水に分散さ
せ、攪拌しながら硫酸及び／又は硫酸アンモニウムを加
えて液のｐＨを８．０±０．５とした後、濾過して乾燥
する方法で製造する擬ベーマイトアルミナを用いれば、
脱窒素活性に優れる脱硫触媒を製造可能であることを見
出し、本発明を完成させた。Means for Solving the Problems The present inventor paid attention to alumina raw materials and made intensive studies. As a result, pseudo-boehmite alumina washed with washing water containing sulfuric acid was formed, and 450 g of alumina was formed.
When a catalyst is produced using a carrier calcined at ~ 650 ° C,
It has been found that the denitrification activity can be greatly improved. Moreover, the desulfurization activity was equivalent to that of a catalyst using a pseudo-boehmite alumina raw material containing no sulfuric acid component. Furthermore, as a result of examining the production conditions of the pseudo-boehmite alumina, it was found that the pH was 8.0.
When the aluminum hydroxide produced in Step 9.5 was filtered off and the obtained aluminum hydroxide cake was washed with sulfuric acid and / or ammonium sulfate-added water, the pH of the filtrate was 8.0.
A method of cleaning and drying so as to be ± 0.5,
The filtered aluminum hydroxide cake is dispersed in water, sulfuric acid and / or ammonium sulfate are added thereto with stirring to adjust the pH of the solution to 8.0 ± 0.5, and then filtered and dried. If boehmite alumina is used,
The inventors have found that a desulfurization catalyst excellent in denitrification activity can be produced, and completed the present invention.
【０００７】[0007]
【発明の実施の形態】本発明の擬ベーマイトアルミナの
製造方法であるが、まず、アルミニウム塩及び／又はア
ルミン酸塩溶液をｐＨ８．０〜９．５で中和して水酸化
アルミニウムの沈殿を作る。アルミニウム塩としては、
硫酸アルミニウム、塩化アルミニウム、硝酸アルミニウ
ム等の任意のアルミニウム塩を用いることができる。ま
た、アルミン酸塩としては、アルミン酸ナトリウム、ア
ルミン酸カリウム等の任意のものを用いることができ
る。中和反応は、アルミニウム塩水溶液に水酸化ナトリ
ウム、水酸化カリウム、アンモニア水等のアルカリ性水
溶液を添加する方法、アルミン酸塩水溶液に硫酸、塩
酸、硝酸等の酸の水溶液を添加する方法、アルミニウム
塩水溶液とアルミン酸塩水溶液を混合する方法のいずれ
を用いても構わないが、製造コストの点から言えばアル
ミニウム塩水溶液とアルミン酸塩水溶液を混合する方法
が好ましい。BEST MODE FOR CARRYING OUT THE INVENTION The method for producing pseudo-boehmite alumina according to the present invention is as follows. First, an aluminum salt and / or aluminate solution is neutralized at pH 8.0 to 9.5 to precipitate aluminum hydroxide. create. As the aluminum salt,
Any aluminum salt such as aluminum sulfate, aluminum chloride, and aluminum nitrate can be used. As the aluminate, any one of sodium aluminate, potassium aluminate and the like can be used. The neutralization reaction is performed by adding an alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, or ammonia water to an aqueous aluminum salt solution, adding an aqueous solution of an acid such as sulfuric acid, hydrochloric acid, or nitric acid to an aqueous aluminate solution; Although any method of mixing the aqueous solution and the aluminate aqueous solution may be used, a method of mixing the aluminum salt aqueous solution and the aluminate aqueous solution is preferable from the viewpoint of production cost.
【０００８】中和反応時のｐＨは８．０〜９．５である
必要がある。ｐＨが９．５を越えると、比表面積の小さ
なバイヤライト相が生成するため、最終的に製造した触
媒の活性が低下することがある。また、ｐＨが８．０を
切ると、得られる擬ベーマイトアルミナの細孔容積が低
下する傾向があり、脱硫触媒に適した擬ベーマイトアル
ミナの製造が難しくなることがある。[0008] The pH during the neutralization reaction needs to be 8.0 to 9.5. When the pH exceeds 9.5, a bayerite phase having a small specific surface area is formed, so that the activity of the finally produced catalyst may decrease. When the pH is less than 8.0, the pore volume of the obtained pseudo-boehmite alumina tends to decrease, and it may be difficult to produce pseudo-boehmite alumina suitable for a desulfurization catalyst.
【０００９】中和沈殿時の温度であるが、５０〜７０℃
の範囲に入っていることが望ましい。温度が５０℃以下
では、粒子が強固に凝集する傾向があり、熟成乾燥工程
を経て得られた粉の細孔容積が小さくなることがある。
また、７０℃以上では、バイヤライトが析出しやすくな
るため、好ましくない。中和沈殿反応の時間であるが、
５分〜６０分間、好ましくは５〜３０分間、さらに好ま
しくは１０〜２５分間の範囲であることが望ましい。こ
の範囲から外れると、得られる擬ベーマイトアルミナ粉
末の細孔容積が０．８ｃｃ／ｇ以下となることがあり、
触媒用擬ベーマイトアルミナとして使用できなくなるこ
とがある。熟成時間に関しては特に制限はないが、生産
効率上から判断して、２時間以内が好ましい。熟成時間
が長過ぎると、擬ベーマイトアルミナ粉の比表面積が小
さくなる傾向がある。The temperature at the time of neutralization precipitation is 50 to 70 ° C.
It is desirable to be within the range. If the temperature is 50 ° C. or lower, the particles tend to agglomerate strongly, and the pore volume of the powder obtained through the aging and drying step may be small.
On the other hand, if the temperature is 70 ° C. or higher, it is not preferable because bayerite is easily precipitated. It is the time of the neutralization precipitation reaction,
It is desirable to be in the range of 5 minutes to 60 minutes, preferably 5 minutes to 30 minutes, more preferably 10 minutes to 25 minutes. Outside this range, the pore volume of the obtained pseudo-boehmite alumina powder may be 0.8 cc / g or less,
In some cases, it cannot be used as pseudo-boehmite alumina for a catalyst. The aging time is not particularly limited, but is preferably 2 hours or less from the viewpoint of production efficiency. If the aging time is too long, the specific surface area of the pseudo-boehmite alumina powder tends to be small.
【００１０】熟成が終了した後、濾過により水酸化アル
ミニウムを濾別する。得られた水酸化アルミニウムケー
キは、中和反応時に副生する塩や、酸、アルカリ等を含
んでいる。このため、これらを洗浄除去するが、本発明
ではこの洗浄水として硫酸及び／又は硫酸アンモニウム
を添加した水を用いることに大きな特徴がある。After aging is completed, the aluminum hydroxide is separated by filtration. The obtained aluminum hydroxide cake contains salts by-produced during the neutralization reaction, acids, alkalis, and the like. For this reason, they are removed by washing. In the present invention, there is a great feature in using water to which sulfuric acid and / or ammonium sulfate is added as the washing water.
【００１１】本発明における洗浄方法の典型例として、
次の２つを挙げることができるが、本発明はこれに限定
されるものではない。 （１）水酸化アルミニウムを濾別した後、ケーキを取り
出す。そのケーキを洗浄容器に移し、水を加えて分散さ
せた後、硫酸及び／又は硫酸アンモニウムを添加し、ｐ
Ｈを８．０±０．５とした後、濾過し乾燥して擬ベーマ
イトアルミナを得る。 （２）水酸化アルミニウムを濾別し直ちに水酸化アルミ
ニウムケーキを硫酸及び／又は硫酸アンモニウム添加水
で洗浄するが、この際、濾液のｐＨが８．０±０．５と
なるように管理して洗浄する。この場合、必要に応じて
水洗工程を加える。その後、乾燥し擬ベーマイトアルミ
ナを得る。As a typical example of the cleaning method in the present invention,
The following two can be cited, but the present invention is not limited to these. (1) After the aluminum hydroxide is filtered off, the cake is taken out. The cake is transferred to a washing vessel and dispersed by adding water, and then sulfuric acid and / or ammonium sulfate are added, and p
After adjusting H to 8.0 ± 0.5, the mixture was filtered and dried to obtain pseudoboehmite alumina. (2) The aluminum hydroxide is filtered off and the aluminum hydroxide cake is immediately washed with sulfuric acid and / or ammonium sulfate-added water. I do. In this case, a washing step is added if necessary. Thereafter, drying is performed to obtain pseudo-boehmite alumina.
【００１２】まず、上記（１）の方法であるが、濾別し
た水酸化アルミニウムケーキを洗浄して、或いは洗浄し
ないまま水酸化アルミニウムケーキを取り出す。その
後、水酸化アルミニウムケーキを別の容器に移し、水を
加えて分散させる。これに硫酸及び／又は硫酸アンモニ
ウムを添加してｐＨを８．０±０．５に調節する。ｐＨ
を調節してから３０分間経過した後に再びｐＨを測定
し、ｐＨの変化が０．３以内、好ましくは０．１以内で
あって、ｐＨが８．０±０．５の範囲内であれば濾過
し、乾燥する。First, in the above method (1), the aluminum hydroxide cake that has been filtered off is washed, or the aluminum hydroxide cake is taken out without washing. Thereafter, the aluminum hydroxide cake is transferred to another container and dispersed by adding water. The pH is adjusted to 8.0 ± 0.5 by adding sulfuric acid and / or ammonium sulfate thereto. pH
30 minutes after the adjustment of the pH, the pH is measured again, and if the change in pH is within 0.3, preferably within 0.1 and the pH is within the range of 8.0 ± 0.5. Filter and dry.
【００１３】乾燥後の擬ベーマイトアルミナに含まれる
アルカリ金属であるが、３０００質量ｐｐｍを越えると
触媒活性に影響が出ることがある。このため、３０００
質量ｐｐｍ以下、好ましくは１０００質量ｐｐｍ以下、
より好ましくは３００質量ｐｐｍ以下にすることが望ま
しい。もし、アルカリ金属イオン濃度が所定値を越えた
場合は、水酸化アルミニウムケーキを洗浄する工程を加
えたり、ケーキを別の容器に移してから行う硫酸及び／
又は硫酸アンモニウム添加水による洗浄操作を複数回繰
り返す等の処理を行う。The alkali metal contained in the pseudo-boehmite alumina after drying. If the content exceeds 3000 ppm by mass, the catalytic activity may be affected. Therefore, 3000
Mass ppm or less, preferably 1000 mass ppm or less,
More preferably, the content is desirably 300 ppm by mass or less. If the alkali metal ion concentration exceeds a predetermined value, a step of washing the aluminum hydroxide cake may be added, or the sulfuric acid and / or
Alternatively, treatment such as repeating a washing operation with ammonium sulfate-added water a plurality of times is performed.
【００１４】しかし、ケーキを別の容器に移してから行
う硫酸及び／又は硫酸アンモニウム添加水による洗浄
は、水酸化アルミニウムを濾過した後に、そのまま水酸
化アルミニウムケーキを洗浄する方法に比較して操作が
煩雑である。このため、水酸化アルミニウムを濾過した
後に、そのまま水酸化アルミニウムケーキを洗浄する方
法を採用するのが好ましい。このようにすることで、水
酸化アルミニウムケーキに含まれるアルカリ金属イオン
濃度を大幅に減少させることができ、後に続く工程であ
るケーキを別の容器に移してから行う硫酸及び／又は硫
酸アンモニウム添加水による洗浄操作が１回で済むばか
りでなく、得られる擬ベーマイトアルミナ中のアルカリ
金属イオン濃度も減少させることができる。[0014] However, the washing with the sulfuric acid and / or ammonium sulfate-added water after transferring the cake to another container is more complicated than washing the aluminum hydroxide cake as it is after filtering the aluminum hydroxide. It is. For this reason, it is preferable to employ a method of washing the aluminum hydroxide cake as it is after filtering the aluminum hydroxide. By doing so, the concentration of alkali metal ions contained in the aluminum hydroxide cake can be significantly reduced, and the subsequent step, in which the cake is transferred to another vessel and then added with sulfuric acid and / or ammonium sulfate added water, is performed. Not only one washing operation is required, but also the alkali metal ion concentration in the obtained pseudo-boehmite alumina can be reduced.
【００１５】水酸化アルミニウムを濾過した後に、その
まま水酸化アルミニウムケーキを洗浄する場合に用いる
洗浄液は、イオン交換水、硫酸添加水、硫酸アンモニウ
ム添加水、塩酸添加水、塩化アンモニウム添加水、硝酸
添加水、硝酸アンモニウム添加水から選ばれる１種以上
を単独で、或いは組み合わせて使用することができる。The washing solution used for washing the aluminum hydroxide cake as it is after filtering the aluminum hydroxide is ion-exchanged water, sulfuric acid added water, ammonium sulfate added water, hydrochloric acid added water, ammonium chloride added water, nitric acid added water, One or more selected from ammonium nitrate added water can be used alone or in combination.
【００１６】ケーキを別の容器に移してから行う硫酸及
び／又は硫酸アンモニウム添加水による洗浄では、水酸
化アルミニウムの沈殿条件、熟成条件、洗浄の有無、洗
浄や濾過時の温度、水酸化アルミニウム量等によりケー
キに含まれるアルカリ金属イオン濃度が大きく変化す
る。このため、使用する硫酸及び／又は硫酸アンモニウ
ム添加水の硫酸分の濃度は一定とはならない。しかし、
硫酸分（添加する硫酸及び硫酸アンモニウム）の濃度が
低すぎると、最終的に擬ベーマイトアルミナ中に含まれ
る硫酸分が不足し、水素化脱硫触媒としたときの脱窒素
活性が十分でなくなることがある。このため、水酸化ア
ルミニウム分散液に含まれる硫酸分の濃度は、０．００
１〜０．２モル／ｌ、好ましくは０．０１〜０．１モル
／ｌとなるように、硫酸と硫酸アンモニウムの添加量を
調節する。つまり、硫酸の添加によってｐＨが８．０±
０．５になった場合でも、体積あたりの硫酸分濃度が
０．００１モル／ｌを切るような場合は、硫酸アンモニ
ウムを添加した液を用いる。In the washing with sulfuric acid and / or ammonium sulfate-added water after transferring the cake to another container, precipitation conditions of aluminum hydroxide, aging conditions, presence or absence of washing, temperature during washing and filtration, amount of aluminum hydroxide, etc. As a result, the concentration of alkali metal ions contained in the cake greatly changes. For this reason, the concentration of the sulfuric acid used in the sulfuric acid and / or ammonium sulfate-added water used is not constant. But,
If the concentration of the sulfuric acid (sulfuric acid and ammonium sulfate to be added) is too low, the sulfuric acid content finally contained in pseudo-boehmite alumina may be insufficient, and the denitrifying activity of the hydrodesulfurization catalyst may not be sufficient. . Therefore, the concentration of sulfuric acid contained in the aluminum hydroxide dispersion is 0.00
The addition amounts of sulfuric acid and ammonium sulfate are adjusted so as to be 1 to 0.2 mol / l, preferably 0.01 to 0.1 mol / l. That is, the pH was adjusted to 8.0 ± by the addition of sulfuric acid.
If the sulfuric acid concentration per volume falls below 0.001 mol / l even when the concentration reaches 0.5, a solution containing ammonium sulfate is used.
【００１７】次に、前記（２）の方法であるが、水酸化
アルミニウムを濾別した後、引き続いて硫酸及び／又は
硫酸アンモニウムを添加した水で濾過洗浄する。そし
て、イオン交換水で濾過洗浄を３０分間行なった時の濾
液のｐＨが８．０±０．５となった時を洗浄の終了とす
る。硫酸及び／又は硫酸アンモニウム添加水の濃度は、
濾液のｐＨが８．０±０．５となるように調製する必要
がある。Next, in the above method (2), after the aluminum hydroxide is filtered off, it is successively filtered and washed with water to which sulfuric acid and / or ammonium sulfate has been added. Then, when the pH of the filtrate obtained after filtration and washing with ion-exchanged water for 30 minutes becomes 8.0 ± 0.5, the washing is completed. The concentration of sulfuric acid and / or ammonium sulfate added water is:
It is necessary to adjust the pH of the filtrate to 8.0 ± 0.5.
【００１８】しかし、洗浄に要する時間、硫酸及び／又
は硫酸アンモニウム添加水の液量、硫酸及び／又は硫酸
アンモニウム添加水中の硫酸濃度、水酸化アルミニウム
の沈殿条件、予備水洗等の水洗条件、温度、水酸化アル
ミニウム量等により大きく変化する。従って、予め予備
試験を行い、硫酸及び／又は硫酸アンモニウム添加水に
よる洗浄条件を決めるのが望ましい。硫酸及び／又は硫
酸アンモニウム添加水中の硫酸分濃度は、初期、中期、
最終の３段階程度に濃度を変えるのが望ましい。通常、
初期洗浄用が０．０００１〜０．０２モル／ｌ、中期洗
浄用が０．０００１〜０．０１モル／ｌ、最終洗浄用が
０．０００１〜０．００５モル／ｌ程度である。However, the time required for washing, the amount of sulfuric acid and / or ammonium sulfate added water, the concentration of sulfuric acid in the sulfuric acid and / or ammonium sulfate added water, aluminum hydroxide precipitation conditions, water washing conditions such as preliminary water washing, temperature, It changes greatly depending on the amount of aluminum and the like. Therefore, it is desirable to carry out a preliminary test in advance to determine the washing conditions using sulfuric acid and / or ammonium sulfate-added water. Sulfuric acid concentration in the sulfuric acid and / or ammonium sulfate added water may be in the initial, middle,
It is desirable to change the concentration in about the last three steps. Normal,
About 0.0001 to 0.02 mol / l for initial washing, about 0.0001 to 0.01 mol / l for middle washing, and about 0.0001 to 0.005 mol / l for final washing.
【００１９】この場合、必要に応じて予備水洗等の水洗
工程を加えることができる。特に水酸化アルミニウムを
濾別した直後に水洗工程を加えると、アルカリ金属イオ
ン濃度を大幅に低下させることができ、濾液のｐＨコン
トロールが容易になる。また、予備水洗を省略した場合
は、硫酸の添加量が多くなり、硫酸及び／又は硫酸アン
モニウム含有洗浄水と接触している部位近傍の水酸化ア
ルミニウムの再溶解が起こりやすくなり、水酸化アルミ
ニウム層の閉塞をきたすことがある。この意味でも予備
水洗工程を加えることが望ましい。In this case, a water washing step such as preliminary water washing can be added if necessary. In particular, if a water washing step is added immediately after the aluminum hydroxide is separated by filtration, the alkali metal ion concentration can be greatly reduced, and the pH control of the filtrate becomes easy. In addition, when the preliminary water washing is omitted, the amount of sulfuric acid added increases, and the aluminum hydroxide in the vicinity of the portion in contact with the sulfuric acid and / or ammonium sulfate-containing washing water tends to be redissolved. May cause blockage. In this sense, it is desirable to add a preliminary washing step.
【００２０】また、乾燥後の擬ベーマイトアルミナに含
まれるアルカリ金属であるが、前記と同様に３０００質
量ｐｐｍ以下、好ましくは１０００質量ｐｐｍ以下、よ
り好ましくは３００質量ｐｐｍ以下にすることが望まし
い。もし、アルカリ金属イオン濃度が所定値を越えた場
合は、水洗処理を加えたり、硫酸及び／又は硫酸アンモ
ニウム添加水による洗浄時間を延長する等の処理条件の
変更を行う。The alkali metal contained in the dried pseudo-boehmite alumina is desirably 3000 mass ppm or less, preferably 1000 mass ppm or less, more preferably 300 mass ppm or less, as described above. If the alkali metal ion concentration exceeds a predetermined value, processing conditions such as adding a water washing treatment or extending the washing time with sulfuric acid and / or ammonium sulfate added water are changed.
【００２１】濾過洗浄中の注意点であるが、水酸化アル
ミニウムケーキは、濾過中に洗浄水がなくなると洗浄水
の編流を起こしやすくなるため、洗浄水は常にケーキ面
より上になるように補充する必要がある。A point to be noted during filtration and washing is that aluminum hydroxide cake is liable to be knitted when washing water runs out during the filtration, so that the washing water is always above the cake surface. Need to refill.
【００２２】以上の洗浄処理後に乾燥するが、スプレー
ドライまたはその他の通常用いられている乾燥装置を使
用することができる。乾燥温度は特に制限はないが、温
度が高すぎると擬ベーマイトアルミナからガンマーアル
ミナへ相転移するため好ましくない。このため、２００
℃以下の通常用いられている温度で乾燥する。このよう
にして製造された擬ベーマイト粉は、窒素吸着法による
全細孔容積が０．８〜１．８ｃｃ／ｇの範囲にある。After the above-mentioned washing treatment, drying is performed. Spray drying or other commonly used drying equipment can be used. The drying temperature is not particularly limited, but if the temperature is too high, the phase transition from pseudo-boehmite alumina to gamma-alumina is not preferable. For this reason, 200
Dry at a commonly used temperature of not more than ℃. The pseudo-boehmite powder thus produced has a total pore volume of 0.8 to 1.8 cc / g by the nitrogen adsorption method.
【００２３】本発明の擬ベーマイトアルミナを用いて触
媒担体を製造する場合は、混練、打錠成形等の通常用い
られている成型方法を用いることができる。特に、混練
法では、細孔容積、細孔分布、平均細孔径等の調整を、
混練時に添加する解膠剤の種類や濃度あるいは混練時間
によってある程度変更可能である。従って、触媒の用途
に応じた担体の製造が可能となる点で好ましい方法であ
る。In the case of producing a catalyst carrier using the pseudo-boehmite alumina of the present invention, a commonly used molding method such as kneading and tablet molding can be used. In particular, in the kneading method, the pore volume, pore distribution, adjustment of the average pore diameter, etc.,
It can be changed to some extent by the type and concentration of the peptizer added during kneading or the kneading time. Therefore, this is a preferable method in that a carrier can be produced according to the use of the catalyst.
【００２４】成形した乾燥品は焼成処理を行うが、焼成
温度は４５０〜６５０℃、好ましくは５００〜６００℃
である。４５０℃を切ると、担体の強度が不十分となる
ことがある。また、６５０℃を越えると触媒としたとき
の活性が十分でなくなることがあり、好ましくない。以
上の本発明による製造方法で得られる担体に含まれる硫
酸分は、硫黄として０．１〜２．０質量％の範囲にな
る。硫酸分濃度をもっと高めたい場合は、硫酸及び／又
は硫酸アンモニウム添加水の硫酸濃度を高めることで対
処可能である。The formed dried product is subjected to a baking treatment at a baking temperature of 450 to 650 ° C, preferably 500 to 600 ° C.
It is. If the temperature is lower than 450 ° C., the strength of the carrier may be insufficient. On the other hand, if the temperature exceeds 650 ° C., the activity as a catalyst may be insufficient, which is not preferable. The sulfuric acid content contained in the carrier obtained by the above-described production method according to the present invention is in the range of 0.1 to 2.0% by mass as sulfur. If it is desired to further increase the sulfuric acid concentration, it can be dealt with by increasing the sulfuric acid concentration of the sulfuric acid and / or ammonium sulfate added water.
【００２５】[0025]
【実施例】以下に本発明の具体的実施例及び比較例を示
す。EXAMPLES Specific examples and comparative examples of the present invention are shown below.
【００２６】（実施例１）内容積１５０ｌの中和沈殿槽
に７５ｌの水を張り、６０℃に加熱しておき、そこに６
０℃に加熱した１モル／ｌのアルミン酸ナトリウム水溶
液を約１．８ｌ／ｍで送液し、同時に６０℃に加熱した
０．５モル／ｌの硫酸アルミニウム水溶液を添加した。
この時のｐＨは９．０±０．１となるように溶液の添加
速度は微調節した。２０分間で送液をやめ、そのままの
温度で、撹拌しつつ１時間熟成して得られたスラリーを
濾過した。水洗後、水酸化アルミニウムケーキを取り出
し、内容積１５０ｌの攪拌槽に入れ、水を７５ｌ加えて
スラリー状とした。これに硫酸を添加し、ｐＨを８．２
に調節した。そのまま攪拌を３０分間続け、ｐＨを測定
したところ、８．１であった。これをスプレードライヤ
ーにて入口／出口温度２００℃/１１０℃で乾燥した。
得られた擬ベーマイトアルミナ粉中のナトリウムは、１
７０質量ｐｐｍ、硫酸分は硫黄として１質量％であっ
た。(Example 1) A neutralization settling tank having an internal volume of 150 liters was filled with 75 liters of water and heated to 60 ° C.
A 1 mol / l sodium aluminate aqueous solution heated to 0 ° C was fed at about 1.8 l / m, and a 0.5 mol / l aqueous aluminum sulfate solution heated to 60 ° C was added at the same time.
The addition rate of the solution was finely adjusted so that the pH at this time was 9.0 ± 0.1. The liquid feeding was stopped in 20 minutes, and the slurry obtained by aging for 1 hour with stirring at the same temperature was filtered. After washing with water, the aluminum hydroxide cake was taken out, put into a stirring tank having an internal volume of 150 l, and 75 l of water was added to form a slurry. To this, sulfuric acid was added to adjust the pH to 8.2.
Was adjusted to Stirring was continued for 30 minutes, and the pH was measured and found to be 8.1. This was dried with a spray dryer at an inlet / outlet temperature of 200 ° C / 110 ° C.
The sodium in the obtained pseudo-boehmite alumina powder was 1
70 mass ppm and the sulfuric acid content was 1 mass% as sulfur.
【００２７】得られた粉をニーダー中で硝酸混練し、固
形分濃度約５０質量％のドウを得た。これを押し出し成
形した後１３０℃で乾燥し、６００℃で１時間焼成して
アルミナ担体を得た。The obtained powder was kneaded with nitric acid in a kneader to obtain a dough having a solid content of about 50% by mass. This was extruded, dried at 130 ° C. and fired at 600 ° C. for 1 hour to obtain an alumina carrier.
【００２８】（比較例１）中和時のｐＨを８．５±０．
１とし、水洗後のケーキを攪拌槽に入れ水だけを加えて
スラリーを得た以外は実施例１と同様にして擬ベーマイ
トアルミナ粉末とアルミナ担体を得た。この擬ベーマイ
トアルミナ粉中のナトリウムは、２９質量ｐｐｍ、硫酸
分は硫黄として０．３５質量％であった。(Comparative Example 1) The pH at the time of neutralization was 8.5 ± 0.5.
The pseudo-boehmite alumina powder and the alumina carrier were obtained in the same manner as in Example 1 except that the cake after water washing was put into a stirring tank and only water was added to obtain a slurry. The sodium in this pseudo-boehmite alumina powder was 29 mass ppm, and the sulfuric acid content was 0.35 mass% as sulfur.
【００２９】（比較例２）市販の擬ベーマイトアルミナ
（Ｐｕｒａｌ ＳＢ；ナトリウムは１０質量ｐｐｍ以
下、硫酸分は硫黄として０．０２質量％）を用い、実施
例１と同様にしてアルミナ担体を得た。Comparative Example 2 An alumina carrier was obtained in the same manner as in Example 1 by using commercially available pseudo-boehmite alumina (Pural SB; 10 mass ppm or less of sodium and 0.02 mass% of sulfuric acid as sulfur). .
【００３０】（比較例３）担体の焼成温度を８００℃と
した以外は実施例１と同様にして擬ベーマイトアルミナ
粉末とアルミナ担体を得た。Comparative Example 3 Pseudo-boehmite alumina powder and an alumina carrier were obtained in the same manner as in Example 1 except that the sintering temperature of the carrier was 800 ° C.
【００３１】触媒調製 実施例及び比較例の担体に、ニッケル、コバルト及びモ
リブデンを含浸させ、脱硫触媒を調製した。含浸液は、
モリブデン酸、ニッケル塩、コバルト塩を含むものを用
いた。含浸後、乾燥し、５５０℃で３０分間焼成し触媒
とした。触媒中のニッケル、コバルト及びモリブデンの
金属換算含有量を表１に示す。 Catalyst Preparation Nickel, cobalt and molybdenum were impregnated into the supports of the Examples and Comparative Examples to prepare desulfurization catalysts. The impregnating liquid is
Those containing molybdic acid, nickel salts and cobalt salts were used. After impregnation, it was dried and calcined at 550 ° C. for 30 minutes to obtain a catalyst. Table 1 shows the metal equivalent contents of nickel, cobalt and molybdenum in the catalyst.
【００３２】[0032]
【表１】 [Table 1]
【００３３】脱窒素活性測定試験 上記触媒を用いて、脱硫及び脱窒素試験を行った。活性
試験に先立ち、触媒は、ＬＨＳＶ ２．０ｈ-1、水素圧
力 ７．８×１０6Ｐａ、水素／Ｏｉｌ比５００ｌ／ｌ
の条件で、１質量％の二硫化炭素を含有する軽油を用
い、３００℃の条件で活性化処理を行った。その後、減
圧軽油を用いて試験を行った。ＬＨＳＶは２．０ｈ-1、
水素圧力は７．８×１０6Ｐａ、水素／Ｏｉｌ比は４０
０ｌ／ｌ、反応温度は３６０℃である。その結果、脱硫
活性はほぼ同等であったが、脱窒素活性は大きな差が出
た。比較例２のＰｕｒａｌ ＳＢを用いて製造した触媒
の活性を１００としたときの相対活性を表２に示す。 Denitrification activity measurement test Desulfurization and denitrification tests were performed using the above catalyst. Prior to the activity test, the catalyst was LHSV 2.0 h -1 , hydrogen pressure 7.8 × 10 6 Pa, hydrogen / oil ratio 500 l / l.
The activation treatment was performed at 300 ° C. using light oil containing 1% by mass of carbon disulfide under the above conditions. Thereafter, a test was performed using vacuum gas oil. LHSV is 2.0h -1 ,
Hydrogen pressure is 7.8 × 10 6 Pa, hydrogen / Oil ratio is 40
0 l / l, reaction temperature 360 ° C. As a result, the desulfurization activities were almost the same, but there was a large difference in the denitrification activities. Table 2 shows the relative activities when the activity of the catalyst produced using Pural SB of Comparative Example 2 was set to 100.
【００３４】[0034]
【表２】 [Table 2]
【００３５】[0035]
【発明の効果】本発明の擬ベーマイトアルミナを用いた
触媒で、硫黄含有石油原料を脱硫、脱窒素処理すると、
従来の触媒に比較して著しく脱窒素活性を高めることが
可能となる。これにより、燃料中の窒素含有量を低減す
ることが可能となり、窒素酸化物による環境汚染の影響
が低減できるようになる。The sulfur-containing petroleum feedstock is desulfurized and denitrified with the catalyst using pseudo-boehmite alumina of the present invention.
It becomes possible to remarkably increase the denitrification activity as compared with a conventional catalyst. As a result, the nitrogen content in the fuel can be reduced, and the effect of environmental pollution due to nitrogen oxides can be reduced.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０１Ｆ 7/34 Ｃ０１Ｆ 7/34 Ｚ 7/74 7/74 Ｃ１０Ｇ 45/08 Ｃ１０Ｇ 45/08 Ｚ ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI C01F 7/34 C01F 7/34 Z 7/74 7/74 C10G 45/08 C10G 45/08 Z
Claims (3)
の水溶液をｐＨ８．０〜９．５で中和し、得られた水酸
化アルミニウムケーキを硫酸及び／又は硫酸アンモニウ
ム添加水で洗浄する際に、濾液のｐＨが８．０±０．５
となるように管理することを特徴とする擬ベーマイトア
ルミナの製造方法。1. An aqueous solution of an aluminum salt and / or an aluminate is neutralized to pH 8.0 to 9.5, and the obtained aluminum hydroxide cake is washed with sulfuric acid and / or ammonium sulfate-added water. PH 8.0 ± 0.5
A method for producing pseudo-boehmite alumina, which is controlled so as to be as follows.
の水溶液をｐＨ８．０〜９．５で中和し、濾別した水酸
化アルミニウムケーキに水と硫酸及び／又は硫酸アンモ
ニウムを添加し、液のｐＨが８．０±０．５となるよう
にすることを特徴とする擬ベーマイトアルミナの製造方
法。2. An aluminum salt and / or aluminate aqueous solution is neutralized to pH 8.0 to 9.5, and water and sulfuric acid and / or ammonium sulfate are added to the filtered aluminum hydroxide cake. Is 8.0 ± 0.5, a method for producing pseudo-boehmite alumina.
イトアルミナから選ばれる１種以上を成形し、４５０〜
６５０℃で焼成することを特徴とする水素化脱硫触媒用
担体の製造方法。3. Molding at least one kind selected from the pseudo-boehmite alumina obtained in claim 1 and 450,
A method for producing a carrier for a hydrodesulfurization catalyst, comprising calcination at 650 ° C.
Priority Applications (1)
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|---|---|---|---|
| JP12470297A JP3945854B2 (en) | 1997-04-30 | 1997-04-30 | Method for producing pseudo-boehmite alumina and method for producing a carrier for hydrodesulfurization catalyst using the pseudo-boehmite alumina |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12470297A JP3945854B2 (en) | 1997-04-30 | 1997-04-30 | Method for producing pseudo-boehmite alumina and method for producing a carrier for hydrodesulfurization catalyst using the pseudo-boehmite alumina |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10310426A true JPH10310426A (en) | 1998-11-24 |
| JP3945854B2 JP3945854B2 (en) | 2007-07-18 |
Family
ID=14891989
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