JPH0353973B2 - - Google Patents
Info
- Publication number
- JPH0353973B2 JPH0353973B2 JP57233963A JP23396382A JPH0353973B2 JP H0353973 B2 JPH0353973 B2 JP H0353973B2 JP 57233963 A JP57233963 A JP 57233963A JP 23396382 A JP23396382 A JP 23396382A JP H0353973 B2 JPH0353973 B2 JP H0353973B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- catalyst
- carrier
- aqueous solution
- 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 - Lifetime
Links
- 239000003054 catalyst Substances 0.000 claims description 28
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 26
- 239000000395 magnesium oxide Substances 0.000 claims description 13
- 150000005846 sugar alcohols Polymers 0.000 claims description 11
- 230000002378 acidificating effect Effects 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000011973 solid acid Substances 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 229920002472 Starch Polymers 0.000 claims description 8
- 235000019698 starch Nutrition 0.000 claims description 8
- 239000008107 starch Substances 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- 238000010304 firing Methods 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 238000004523 catalytic cracking Methods 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 230000000694 effects Effects 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical group CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical class [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- -1 lactic acid Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Hydrogen, Water And Hydrids (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
本発明は、石油系炭化水素の接触分解用Ni系
触媒の製造方法に関する。
重質油の水素化分解、灯軽油、重油、原油等の
接触分解に使用される触媒としては、マグネシア
担体に触媒活性成分としてのNiを担持させた触
媒が主に用いられている。しかしながら、現在工
業的規模で使用されているNi系触媒は、経年的
にカーボン付着による破損を生じやすく、汚染物
の付着及び触媒表面からの触媒活性成分の脱離に
よる活性の低下も避け難い。
本発明者は、工業的規模の使用条件において
も、カーボン付着による破壊を生ずることなく、
長期にわたり高活性を持続し得るNi系触媒を得
るべく種々研究を重ねた結果、マグネシア担体の
製造に際し特定の弱酸性固体酸及び多価アルコー
ルを粘結剤として併用する場合には、得られた担
体の強度延いてはNi系触媒の強度が著しく向上
し、触媒活性の低下も著しく軽減されることを見
出した。即ち、本発明は下記の石油系炭化水素の
接触分解用Ni系触媒の製造法を提供するもので
ある。
マグネシア粉体100重量部に、シユウ酸及び
ホウ酸からなる弱酸性固体酸の少なくとも１種
の水溶液又は分散液を固形分として0.5〜2.0重
量部、及びポリビニルアルコール及びデンプン
からなる多価アルコールの少なくとも１種の水
溶液又は分散液をアルコール分として0.5〜2.0
重量部を加えて均一に混練し、造粒し、焼成し
て担体とした後、該担体にNiを担持させるこ
とを特徴とする石油系炭化水素の接触分解用
Ni系触媒の製造法。
本発明においては、マグネシア粉体を担体原料
として使用する。担体原料100重量部中には５重
量部までのシリカ、鉄、カルシウムの酸化物等を
含んでいても良い。
本発明においては、水溶液又は水分酸液の形態
でシユウ酸及びホウ酸からなる弱酸性固体酸の少
なくとも１種を使用する。弱酸性固体酸は、マグ
ネシア粉体100重量部に対し、固形分として0.5〜
2.0重量部使用する。弱酸性固体酸の量が0.5重量
部未満の場合には、強度改善の効果が十分に発揮
されず、一方、2.0重量部を上回る場合には、粘
度が上り、造粒しにくくなり、また実際に使用し
た場合、触媒粒子同志が熔融固着するという欠点
もある。上記の弱酸性固体酸は、10〜30重量％程
度の水溶液又は水分散液として使用することが好
ましい。
多価アルコールとしては、ポリビニルアルコー
ル（PVA）及びデンプンからなる多価アルコー
ルの少なくとも１種を水溶液又は水分散液の状態
で使用する。上記ポリビニルアルコールは、バイ
ンダーとして汎用されている重合度1000〜1600程
度、けん化度85〜90程度のものを用いることが好
ましい。また、上記デンプンとしても、常用され
ているデンプン系バインダー、例えば特公昭46−
43363号公報に開示されているもの、より具体的
にはデンプンを物理的及び化学的処理（例えば、
乳酸、錯酸、クエン酸の如き有機酸又は無機酸に
よる処理）し、次いで100〜300℃の温度において
加熱して得られるものなどを使用する。多価アル
コール使用量は、マグネシア粉体100重量部に対
しアルコール分として0.5〜2.0重量部である。多
価アルコールの量が0.5重量部未満の場合には、
気孔率が下り、一方、2.0重量部を上回る場合に
は、触媒の強度低下が著しい。
本発明方法は、以下の様にして実施する。所定
粒度のマグネシア粉体に所定量の弱酸性固体酸及
び多価アルコールを水溶液又は水分散液の形態で
加え、均一に混練した後、所定の粒径、通常10〜
25mm程度に造粒する。次いで造粒物を乾燥後、大
気中1300〜1400℃程度、より好ましくは1330〜
1370℃程度で焼成してマグネシア担体とする。本
発明における担体製造時の焼成温度は、従来法に
おける焼成温度に比して150〜200℃程度低く、こ
の点も本発明の大きな利点である。かくして得ら
れたマグネシア担体を常法に従つて硝酸ニツケ
ル、塩化ニツケル等のニツケル化合物の水溶液に
浸漬した後、乾燥し、大気中600〜650℃程度で焼
成してNi触媒とする。ニツケルの担持量は、通
常マグネシア担体重量の1.0〜3.0％程度である。
本発明方法によれば、次の様な効果が奏され
る。
() 担体製造時の焼成温度が、従来法のそれに
比して低いので、設備上及びエネルギー上の経
費節減が可能となる。又、焼成時の破損が少な
いので、担体収率が向上する。
() 触媒の初期活性は、従来方法により製造さ
れた触媒の場合と変らない。
() 長時間使用後のカーボン析出による破損や
粉化が効果的に防止され、その結果触媒寿命が
延長される。
() 長時間使用後の活性低下が、公知触媒に比
して、緩和される。
実施例 １
微粉砕したMgO粉体100重量部に下記第１表に
示す割合で弱酸性固体酸及び多価アルコールを加
え、均一に混練し、約14mmに造粒し、乾燥した。
乾燥物を大気中約1350℃で２時間焼成して得た
MgO担体を濃度20％の硝酸ニツケル水溶液に２
時間浸漬した後、乾燥し、大気中で約650℃で２
時間焼成してNi担持触媒を得た。尚、本実施例
では多価アルコールとして、ポリビニルアルコー
ルは重合度約1500、けん化度約86のものを用い、
デンプンは予めクエン酸による処理によつてデン
プンの表皮を破壊した後、100〜300℃の温度にお
いて加熱したものを用いた。
かくして得られたNi触媒を径100mm、長さ1000
mmの反応管に収容し、800℃及び900℃でプロパン
の水蒸気分解に使用し、プロパン1Nm3当りの生
成ガス（Ｎm3）をもつて初期活性を判定した。
又、得られたNi触媒を使用して、クウエート
原油をLHSV＝0.6／hr、水蒸気／油（Kg／Kg）
＝1.2、触媒層温度890〜910℃、反応圧力＝常圧、
触媒充填量170の条件下に水蒸気分解し、触媒
の粉化率を調べた。尚、クウエート原油の性状
は、比重（15／４℃）＝0.8685、初留点＝50℃で
あつた。
第１表に触媒の物性、初期活性及び8000時間使
用後の粉化率を示す。
尚、第１表には、粘結剤を全く使用しない場合
（比較例１）、弱酸性固体酸のみを使用する場合
（比較例２）、多価アルコールのみを使用する場合
（比較例３）、粘結剤を使用することなく高温
（1100℃）で担体を焼成した場合（比較例４）の
結果を併せて示す。触媒製造時の焼成温度は、比
較例４のみが1100℃であり、他は全て650℃であ
る。
The present invention relates to a method for producing a Ni-based catalyst for catalytic cracking of petroleum hydrocarbons. Catalysts used in the hydrocracking of heavy oil, catalytic cracking of kerosene, heavy oil, crude oil, etc. are mainly catalysts in which Ni is supported as a catalytically active component on a magnesia carrier. However, Ni-based catalysts currently used on an industrial scale tend to be damaged over time due to carbon adhesion, and a decrease in activity due to the adhesion of contaminants and desorption of catalytic active components from the catalyst surface is also unavoidable. The present inventor has discovered that even under industrial-scale usage conditions, there is no damage caused by carbon adhesion.
As a result of various studies to obtain a Ni-based catalyst that can maintain high activity over a long period of time, we have found that when a specific weakly acidic solid acid and polyhydric alcohol are used together as a binder during the production of magnesia carriers, the following results were obtained: It has been found that the strength of the support and, in turn, the strength of the Ni-based catalyst are significantly improved, and the decline in catalyst activity is significantly reduced. That is, the present invention provides the following method for producing a Ni-based catalyst for catalytic cracking of petroleum hydrocarbons. 100 parts by weight of magnesia powder, 0.5 to 2.0 parts by weight of at least one aqueous solution or dispersion of a weakly acidic solid acid consisting of oxalic acid and boric acid, and at least 0.5 to 2.0 parts by weight of a polyhydric alcohol consisting of polyvinyl alcohol and starch. Alcohol content of one type of aqueous solution or dispersion is 0.5 to 2.0
For catalytic cracking of petroleum hydrocarbons, which is characterized by adding parts by weight, uniformly kneading, granulating, and firing to form a carrier, and then supporting Ni on the carrier.
Manufacturing method of Ni-based catalyst. In the present invention, magnesia powder is used as a carrier raw material. Up to 5 parts by weight of silica, iron, calcium oxides, etc. may be contained in 100 parts by weight of the carrier raw material. In the present invention, at least one weakly acidic solid acid consisting of oxalic acid and boric acid is used in the form of an aqueous solution or a water acid solution. Weakly acidic solid acid has a solid content of 0.5 to 100 parts by weight of magnesia powder.
Use 2.0 parts by weight. If the amount of the weakly acidic solid acid is less than 0.5 parts by weight, the strength improvement effect will not be fully exhibited, while if it exceeds 2.0 parts by weight, the viscosity will increase, making granulation difficult, and There is also a drawback that when used in a catalyst, the catalyst particles are melted and stuck to each other. The above-mentioned weakly acidic solid acid is preferably used as an aqueous solution or dispersion of about 10 to 30% by weight. As the polyhydric alcohol, at least one polyhydric alcohol consisting of polyvinyl alcohol (PVA) and starch is used in the form of an aqueous solution or an aqueous dispersion. The polyvinyl alcohol preferably has a degree of polymerization of about 1000 to 1600 and a degree of saponification of about 85 to 90, which is commonly used as a binder. The above-mentioned starch may also be a commonly used starch-based binder, such as
43363, more specifically, starch is subjected to physical and chemical treatments (e.g.
Treatment with an organic or inorganic acid such as lactic acid, complex acid, or citric acid) and then heating at a temperature of 100 to 300°C are used. The amount of polyhydric alcohol used is 0.5 to 2.0 parts by weight as alcohol content per 100 parts by weight of magnesia powder. If the amount of polyhydric alcohol is less than 0.5 parts by weight,
The porosity decreases, and on the other hand, if it exceeds 2.0 parts by weight, the strength of the catalyst decreases significantly. The method of the present invention is carried out as follows. A predetermined amount of a weakly acidic solid acid and a polyhydric alcohol in the form of an aqueous solution or aqueous dispersion are added to magnesia powder of a predetermined particle size, and after uniformly kneading, the powder is powdered to a predetermined particle size, usually 10~
Granulate to approximately 25mm. Next, after drying the granules, the temperature is about 1300 to 1400°C in the atmosphere, more preferably 1330 to 1400°C.
It is fired at around 1370℃ to form a magnesia carrier. The firing temperature during the production of the carrier in the present invention is about 150 to 200°C lower than that in conventional methods, and this point is also a great advantage of the present invention. The thus obtained magnesia carrier is immersed in an aqueous solution of a nickel compound such as nickel nitrate or nickel chloride according to a conventional method, dried, and calcined in the atmosphere at about 600 to 650°C to obtain a Ni catalyst. The amount of nickel supported is usually about 1.0 to 3.0% of the weight of the magnesia carrier. According to the method of the present invention, the following effects are achieved. () Since the firing temperature during carrier production is lower than that of conventional methods, it is possible to save on equipment and energy costs. Furthermore, since there is less damage during firing, the carrier yield is improved. () The initial activity of the catalyst is the same as that of catalysts produced by conventional methods. () Breakage and powdering caused by carbon deposition after long-term use are effectively prevented, resulting in extended catalyst life. () Deterioration in activity after long-term use is alleviated compared to known catalysts. Example 1 A weakly acidic solid acid and a polyhydric alcohol were added to 100 parts by weight of finely pulverized MgO powder in the proportions shown in Table 1 below, and the mixture was uniformly kneaded, granulated to about 14 mm, and dried.
Obtained by baking the dried product in the air at approximately 1350℃ for 2 hours.
MgO carrier is added to a nickel nitrate aqueous solution with a concentration of 20%.
After soaking for an hour, dry it in the air at about 650℃ for 2 hours.
A Ni-supported catalyst was obtained by firing for a period of time. In this example, polyvinyl alcohol with a degree of polymerization of about 1500 and a degree of saponification of about 86 was used as the polyhydric alcohol.
The starch used was one that had been heated at a temperature of 100 to 300°C after the outer skin of the starch had been destroyed by treatment with citric acid. The Ni catalyst obtained in this way was 100 mm in diameter and 1000 mm in length.
The reactor was placed in a reaction tube of 1.5 mm in diameter and used for steam decomposition of propane at 800° C. and 900° C., and the initial activity was determined based on the amount of gas produced (Nm 3 ) per 1 Nm 3 of propane. In addition, using the obtained Ni catalyst, Kuwaiti crude oil was converted to LHSV=0.6/hr, water vapor/oil (Kg/Kg)
= 1.2, catalyst layer temperature 890-910℃, reaction pressure = normal pressure,
Steam decomposition was carried out under conditions of a catalyst loading of 170, and the powdering rate of the catalyst was investigated. The Kuwaiti crude oil had a specific gravity (15/4°C) of 0.8685 and an initial boiling point of 50°C. Table 1 shows the physical properties, initial activity, and powdering rate of the catalyst after 8000 hours of use. Table 1 shows cases in which no binder is used at all (Comparative Example 1), cases in which only weakly acidic solid acids are used (Comparative Example 2), and cases in which only polyhydric alcohol is used (Comparative Example 3). Also shown are the results obtained when the carrier was fired at high temperature (1100° C.) without using a binder (Comparative Example 4). The firing temperature during catalyst production was 1100°C only in Comparative Example 4, and 650°C in all others.
【表】
第１表に示す結果から明らかな如く、本発明方
法により製造された触媒は、担体製造時の焼成温
度が低いにもかかわらず、圧縮強度が高く、活性
に優れ、長時間使用後にも粉化し難いことが明ら
かである。[Table] As is clear from the results shown in Table 1, the catalyst produced by the method of the present invention has high compressive strength and excellent activity despite the low calcination temperature during carrier production, and even after long-term use. It is clear that it is also difficult to powder.
Claims (1)
ホウ酸からなる弱酸性固体酸の少なくとも１種の
水溶液又は分散液を固形分として0.5〜2.0重量
部、及びポリビニルアルコール及びデンプンから
なる多価アルコールの少なくとも１種の水溶液又
は分散液をアルコール分として0.5〜2.0重量部を
加えて均一に混練し、造粒し、焼成して担体とし
た後、該担体にNiを担持させることを特徴とす
る石油系炭化水素の接触分解用Ni系触媒の製造
法。1 100 parts by weight of magnesia powder, 0.5 to 2.0 parts by weight of at least one aqueous solution or dispersion of a weakly acidic solid acid consisting of oxalic acid and boric acid, and a polyhydric alcohol consisting of polyvinyl alcohol and starch. A petroleum oil characterized by adding 0.5 to 2.0 parts by weight of at least one aqueous solution or dispersion as an alcohol content, uniformly kneading it, granulating it, and firing it to form a carrier, and then making the carrier support Ni. A method for producing a Ni-based catalyst for catalytic cracking of hydrocarbons.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57233963A JPS59120242A (en) | 1982-12-24 | 1982-12-24 | Preparation of ni-type catalyst for catalytic cracking of petroleum hydrocarbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57233963A JPS59120242A (en) | 1982-12-24 | 1982-12-24 | Preparation of ni-type catalyst for catalytic cracking of petroleum hydrocarbon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59120242A JPS59120242A (en) | 1984-07-11 |
| JPH0353973B2 true JPH0353973B2 (en) | 1991-08-16 |
Family
ID=16963370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57233963A Granted JPS59120242A (en) | 1982-12-24 | 1982-12-24 | Preparation of ni-type catalyst for catalytic cracking of petroleum hydrocarbon |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59120242A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4663098B2 (en) * | 2000-11-08 | 2011-03-30 | 石油資源開発株式会社 | Production method of hydrogen |
| JP4663103B2 (en) * | 2000-12-06 | 2011-03-30 | 独立行政法人石油天然ガス・金属鉱物資源機構 | Syngas production |
| JP4663104B2 (en) * | 2000-12-06 | 2011-03-30 | 石油資源開発株式会社 | Syngas production by autothermal reforming |
-
1982
- 1982-12-24 JP JP57233963A patent/JPS59120242A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59120242A (en) | 1984-07-11 |
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