JPH11156198A - Hydrogenation cracking catalyst for medium duty distilled oil production - Google Patents
Hydrogenation cracking catalyst for medium duty distilled oil productionInfo
- Publication number
- JPH11156198A JPH11156198A JP10256647A JP25664798A JPH11156198A JP H11156198 A JPH11156198 A JP H11156198A JP 10256647 A JP10256647 A JP 10256647A JP 25664798 A JP25664798 A JP 25664798A JP H11156198 A JPH11156198 A JP H11156198A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- zeolite
- weight
- alumina
- acidity
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- 238000005336 cracking Methods 0.000 title abstract description 13
- 238000005984 hydrogenation reaction Methods 0.000 title abstract description 12
- 238000004519 manufacturing process Methods 0.000 title abstract description 11
- 239000011959 amorphous silica alumina Substances 0.000 claims abstract description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 12
- 238000001179 sorption measurement Methods 0.000 claims abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000003075 superhydrophobic effect Effects 0.000 claims abstract description 8
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 27
- 239000011148 porous material Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- 239000010457 zeolite Substances 0.000 claims description 24
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 21
- 229910021536 Zeolite Inorganic materials 0.000 claims description 20
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 12
- 230000002378 acidificating effect Effects 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 150000004706 metal oxides Chemical class 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 238000010335 hydrothermal treatment Methods 0.000 claims description 7
- 238000010306 acid treatment Methods 0.000 claims description 5
- 230000009615 deamination Effects 0.000 claims description 5
- 238000006481 deamination reaction Methods 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002283 diesel fuel Substances 0.000 abstract description 12
- 230000008014 freezing Effects 0.000 abstract description 7
- 238000007710 freezing Methods 0.000 abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 5
- 238000004821 distillation Methods 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 229910018404 Al2 O3 Inorganic materials 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 35
- 238000006243 chemical reaction Methods 0.000 description 16
- 230000008569 process Effects 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000003350 kerosene Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 101150076749 C10L gene Proteins 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229940095674 pellet product Drugs 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7815—Zeolite Beta
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Combustion Methods Of Internal-Combustion Engines (AREA)
- Catalysts (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、水素化分解触媒、
特に、中質留出油生産のための水素化分解触媒に関す
る。[0001] The present invention relates to a hydrocracking catalyst,
In particular, it relates to a hydrocracking catalyst for the production of medium distillate.
【０００２】[0002]
【従来の技術】現在、世界の精油所では、精油する原料
が重質化しており、品質も低下するという問題に直面し
ており、それだけに水素化分解プロセスが、重質油を軽
質化するための最も重要な手段の１つとして注目されて
いる。世界の中質留出油に対する需要は、継続的に増加
しており、それに伴い、中質留出油生産のための水素化
触媒、特に、航空灯油、ディーゼル油などの中質留出油
を、その設備能力の上限まで生産させる機能があり、し
かも、運転使用に関しての柔軟性のある水素化分解触媒
の開発が活発化している。2. Description of the Related Art At present, refineries in the world are facing the problem that the raw material to be refined is heavier and the quality is deteriorated. Therefore, the hydrocracking process is required to lighten the heavy oil. Is attracting attention as one of the most important means. Demand for heavy distillates worldwide is continually increasing, and as a result, hydrogenation catalysts for the production of medium distillates, especially heavy distillates such as aviation kerosene and diesel oil, are being used. The development of a hydrocracking catalyst which has a function of producing up to the upper limit of the facility capacity and has flexibility in terms of operation and use has been activated.
【０００３】水素化分解触媒は、水素化とクラッキング
機能の両方を有する二元機能触媒である。従来の非貴金
属系の水素化分解触媒の場合、周期表第VIｂ族、第VIII
族金属が、水素化成分として一般に使用され、結晶ゼオ
ライトおよび/または無定形シリカ-アルミナが酸性成分
として選択されている。無定形シリカ-アルミナを単独
に使用した場合には、それ自体、高い選択性を有するけ
れども、その触媒活性は低く、使用上の融通性も低い。
そこで、新規のゼオライト材料を導入することで、これ
ら２つの材料を組み合わせて使用して、中質油に対する
高い触媒活性と選択性を有する新しい型の水素化触媒を
得ることができる。[0003] Hydrocracking catalysts are bifunctional catalysts that have both hydrogenation and cracking functions. In the case of conventional non-noble metal-based hydrocracking catalysts, groups VIb and VIII of the periodic table
Group metals are commonly used as the hydrogenation component, with crystalline zeolites and / or amorphous silica-alumina being selected as the acidic component. When amorphous silica-alumina is used alone, it itself has high selectivity, but has low catalytic activity and low flexibility in use.
Thus, by introducing a new zeolite material, a new type of hydrogenation catalyst having high catalytic activity and selectivity for intermediate oils can be obtained using these two materials in combination.
【０００４】従来技術においては、水素化触媒のための
結晶性ゼオライトは、細孔径の大きいゼオライト、例え
ば、ゼオライト-Ｘ、-Ｙ、好ましくは、ゼオライト-Ｙ
で構成されている。この触媒では、高分子炭化水素が、
そこで転化されるゼオライトの細孔に入り込むことにな
る。パラフィン・ベースの原料の場合、３４３℃以上の
留分が１６５〜３４３℃の留分にクラッキングされて得
られるディーゼル油は凍結温度が高く、したがって中質
留出油の収率も低下する。別の型のクラッキング触媒と
して、例えば、ＺＳＭ-５のような細孔径の小さいゼオ
ライトまたは形状選択性ゼオライトをクラッキング成分
として使用したものがあるが、ゼオライトの細孔構造に
入ることができるのは、直鎖または短い側鎖を持つアル
カンだけであり、例えば、直鎖の炭化水素類だけが転化
され脱ロウされることになり、したがって、ディーゼル
油とテール油では、その凍結温度は低くなる。このゼオ
ライトでは細孔が小さいために、反応物が時間内に除去
されず、その結果として、過剰なクラッキングが起こ
り、中質油に対する選択性が低下してしまう。さらに、
高分子量の炭化水素は、細孔に入ることができない。特
に、重質の原料を扱うときには、触媒活性が低下してし
まう。In the prior art, crystalline zeolites for hydrogenation catalysts are zeolites of large pore size, for example zeolite-X, -Y, preferably zeolite-Y.
It is composed of In this catalyst, high molecular hydrocarbons are
There, it enters the pores of the converted zeolite. In the case of paraffin-based feedstocks, the diesel oil obtained by cracking a fraction above 343 ° C. into a fraction between 165 ° C. and 343 ° C. has a high freezing temperature and therefore a low yield of medium distillate. Another type of cracking catalyst includes, for example, a zeolite with a small pore size such as ZSM-5 or a shape-selective zeolite as a cracking component. Only alkanes with straight or short side chains, for example, only straight chain hydrocarbons will be converted and dewaxed, so that diesel and tail oils have lower freezing temperatures. Due to the small pores of this zeolite, the reactants are not removed in time, resulting in excessive cracking and reduced selectivity for medium oils. further,
High molecular weight hydrocarbons cannot enter the pores. In particular, when handling heavy raw materials, the catalytic activity is reduced.
【０００５】「中国精油所技術」(Hou Xiang-lin氏監修、
pp.511、SINOPECプレス)には、#３８１２触媒について
開示されている。この触媒は、重質原料油を処理して、
水素化分解と水素化脱ロウを同時に行うことにより、プ
レミアム中質留出油、低凍結温度ディーゼル油、潤滑基
油を生産する場合に使用されるものである。この触媒の
特徴は、ゼオライト-βを使用していることである。こ
の触媒を使用して得られた水素化分解産物の品質は良い
が、この触媒を重質原料油の処理に使用するとき、反応
温度は一般に３９０℃以上が必要である。例えば、３９
３℃の反応温度で、Daqing VGOを処理すると、ナフサな
どの軽質油が生産可能であるが、一段転化率が７０wt
%、ガスとガソリンの収率が２７.９wt%であり、中質油
に対する選択性は低い。[0005] "China refinery technology" (supervised by Hou Xiang-lin,
pp. 511, SINOPEC Press) discloses a # 3812 catalyst. This catalyst processes heavy feedstock,
It is used to produce premium medium distillate, low freezing temperature diesel oil, and lubricating base oil by simultaneously performing hydrocracking and hydrodewaxing. The feature of this catalyst is that zeolite-β is used. The quality of the hydrocracked product obtained using this catalyst is good, but when this catalyst is used for the treatment of heavy feedstock, the reaction temperature generally needs to be 390 ° C. or higher. For example, 39
By treating Daqing VGO at a reaction temperature of 3 ° C, light oil such as naphtha can be produced, but the single-stage conversion rate is 70 wt%.
%, The yield of gas and gasoline is 27.9 wt%, and the selectivity to medium oil is low.
【０００６】米国特許４,８２０,４０２には、水素化分
解プロセスが開示されている。ここでは、酸性成分とし
てＳiＯ2/Ａl2Ｏ3の含有比率の高いゼオライトを使用す
ることにより、１６５〜３４３℃の範囲にある留出油製
品の生産での改良された選択性が得られている。この特
許では、中質油に対する選択性を増加させ水素消費量を
減らすためには、触媒中のゼオライト成分のシリカ/ア
ルミナのモル比が、少なくとも５０:１,好ましくは１０
０:１,より好ましくは２００:１であることが必要と記
載されている。この特許により開示された触媒を、転化
率が６０ｖ%に制御された条件下で、Arabian VGOを処理
する場合に使用すると、中質油に対する選択率は４５〜
６５ｖ%となる。US Pat. No. 4,820,402 discloses a hydrocracking process. Here, by using a high content ratio of SiO 2 / Al 2 O 3 zeolite as the acidic component, obtained an improved selectivity in the production of distillate product in the range of one hundred and sixty-five to three hundred and forty-three ° C. I have. In this patent, the zeolite component silica / alumina molar ratio in the catalyst is at least 50: 1, preferably 10: 1, in order to increase selectivity to medium oils and reduce hydrogen consumption.
0: 1, more preferably 200: 1. When the catalyst disclosed by this patent is used in treating Arabian VGO under controlled conditions of 60 v% conversion, the selectivity to medium oil is 45-45.
It becomes 65v%.
【０００７】触媒に使用されるＳiＯ2/Ａl2Ｏ3の高い含
有比(ＳiＯ2/Ａl2Ｏ3=２００:１)の別のゼオライトで
は、中質油に対して違った選択性を示し、その順序は高
いほうから、ＺＳＭ-２０＞ゼオライト-β＞ゼオライト
-Ｙとなっている。最も良好なものは、ＺＳＭ-２０を含
む触媒であり、その選択率は、空間速度が０.５４hrー1
の条件下で、中質油に対して７２ｖ%である。ゼオライ
ト-βが酸性成分として使用され、転化率が６０ｖ%であ
る場合には、中質油に対する選択率は７０ｖ%以下であ
る。[0007] high content ratio of SiO 2 / Al 2 O 3 used in the catalyst (SiO 2 / Al 2 O 3 = 200: 1) In another zeolite, shows a different selectivity for middle fraction oil ZSM-20>Zeolite-β> Zeolite
-Y. The best is a catalyst containing ZSM-20, which has a selectivity at a space velocity of 0.54 hr -1.
Under the conditions described above, 72 v% based on the medium oil. If zeolite-β is used as the acidic component and the conversion is 60 v%, the selectivity to medium oil is below 70 v%.
【０００８】ＥＰ００２８９３８には、ゼオライト-Ｙ
ＵＨＰ-Ｙからなる水素化分解触媒について述べられて
おり、この触媒を使用しArabian VGOを処理すると、中
質油に対するその選択率は８６ｖ%であるが、その転化
率はわずかに６０ｖ%である。クラッキングが容易であ
るKuwait VGOを処理する場合には、反応温度は４０７℃
という高い温度となる。この反応温度を３９７℃に下げ
ると、中質油に対する選択率はわずか７４ｖ%になる。[0008] EP0028938 includes zeolite-Y
A hydrocracking catalyst consisting of UHP-Y is described, and when this catalyst is used to treat Arabian VGO, its selectivity to medium oil is 86 v%, but its conversion is only 60 v%. . When processing Kuwait VGO, which is easy to crack, the reaction temperature is 407 ° C.
High temperature. When the reaction temperature is reduced to 397 ° C., the selectivity to medium oil is only 74 v%.
【０００９】[0009]
【発明が解決しようとする課題】本発明の目的は、重質
炭化水素原料を処理して、中質留出油の生産に使用でき
る中質油水素化分解触媒を提供することである。本発明
のさらに別の目的は、高い触媒活性、中質油に対する高
い選択性、使用上の融通性、上限までの設備能力で、高
い煙点の航空灯油と、広い留出範囲と低い凍結温度を有
するディーゼル油を生産させる能力を有する主酸性成分
としてのゼオライト-βからなる中質油水素化分解触媒
を提供することである。SUMMARY OF THE INVENTION It is an object of the present invention to provide a medium oil hydrocracking catalyst which can be used for the production of medium distillates by treating heavy hydrocarbon feedstocks. Yet another object of the present invention is to provide a high smoke point aviation kerosene, a high distillation range and a low freezing temperature, with high catalytic activity, high selectivity to medium oils, It is an object of the present invention to provide a medium oil hydrocracking catalyst comprising zeolite-β as a main acidic component having the ability to produce a diesel oil having the following characteristics.
【００１０】[0010]
【課題を解決するための手段】本発明の触媒は、主酸性
成分としての変性ゼオライト-β、追加の酸性成分およ
びキャリヤとしての無定形シリカ-アルミナ、そして、
水素化成分として、周期表第VIｂ族から選択される少な
くとも１個の担持される金属および第VIII族から選択さ
れる少なくとも１個の担持される金属からなる。本発明
の触媒の比表面積は２００〜３００m2/g、細孔容積は
０.３〜０.４ml/g、ピリジン吸着ＩＲ法により測定した
酸性度(以下、酸性度)は０.３〜０.５mmol/gである。本
発明に係る触媒の変性ゼオライト-βの酸性度は０.１〜
０.５mmol/g、ＳiＯ2/Ａl2Ｏ3の含有比率(化学法)は３
０〜９０、Ｎa2Ｏ含有率が＜０.２wt%である。SUMMARY OF THE INVENTION The catalyst of the present invention comprises modified zeolite-β as the main acidic component, amorphous silica-alumina as the additional acidic component and carrier, and
The hydrogenation component consists of at least one supported metal selected from group VIb of the periodic table and at least one supported metal selected from group VIII. The specific surface area of the catalyst of the present invention is 200 to 300 m 2 / g, the pore volume is 0.3 to 0.4 ml / g, and the acidity (hereinafter, acidity) measured by pyridine adsorption IR method is 0.3 to 0. It is 0.5 mmol / g. The modified zeolite-β of the catalyst according to the present invention has an acidity of 0.1 to 0.1.
0.5 mmol / g, the content ratio of SiO 2 / Al 2 O 3 (chemical method) is 3
0 to 90, Na 2 O content is <0.2 wt%.
【００１１】本発明に係る触媒は、５〜４０wt%の変性
ゼオライト-β、１０〜 50wt%の無定型シリカ-アルミ
ナ、１５〜３０wt%(乾燥アルミナとして計算)のバイン
ダー、１０〜４０wt%の第VIｂ族金属(好ましくは、Ｍo
および/またはＷ)、１〜１０ｗｔ%(金属酸化物として計
算)の第VIII族金属(好ましくは、Ｃoおよび/またはＮi)
からなる。The catalyst according to the invention comprises 5 to 40% by weight of modified zeolite-β, 10 to 50% by weight of amorphous silica-alumina, 15 to 30% by weight of binder (calculated as dry alumina), 10 to 40% by weight of Group VIb metal (preferably, Mo
And / or W) 1-10 wt% (calculated as metal oxide) of Group VIII metal (preferably Co and / or Ni)
Consists of
【００１２】従来技術では、このゼオライト-βは、下
記の２つのステップを経ることで、ＳiＯ2/Ａl2Ｏ3の含
有比率を増加させ、変性することが可能となる。１.
高温でのカ焼による脱アミノ化:有機アミン鋳型(templa
te agent)を除去するために５００〜６００℃で数時間
ゼオライト-βをカ焼するステップ。２. 酸処理による
脱アルミ化:ＳiＯ2/Ａl2Ｏ3の含有比率を増加させるた
めに、特定の温度で、ある濃度の無機酸とゼオライト-
βを反応させ、ゼオライト-βの骨格からアルミニウム
を除去するステップ。According to the prior art, this zeolite-β can be modified by increasing the content ratio of SiO 2 / Al 2 O 3 through the following two steps. 1.
Deamination by calcination at high temperature: organic amine template (templa
calcining zeolite-β at 500-600 ° C for several hours to remove te agent). 2. Dealumination by acid treatment: In order to increase the content ratio of SiO 2 / Al 2 O 3 , a certain concentration of inorganic acid and zeolite at a specific temperature.
reacting β to remove aluminum from the framework of zeolite-β.
【００１３】高温でのカ焼により脱アミノ化させた後、
出発材料のゼオライト-βの酸性度を０.８〜１.０mmol/
gに低下させ、その後、酸の処理により脱アルミ化を行
った後、ゼオライト-βの酸性度を０.５〜０.６mmol/g
に低下させる。上記の変性ゼオライト-βの固体酸の量
をある程度低下させることができるが、中質油に対する
選択性を実質的に増加させるには十分でない。After deamination by calcination at high temperature,
The acidity of the starting zeolite-β is 0.8-1.0 mmol /
g, and after dealumination by acid treatment, the acidity of zeolite-β is adjusted to 0.5 to 0.6 mmol / g.
To lower. Although the amount of solid acid of the above modified zeolite-β can be reduced to some extent, it is not enough to substantially increase the selectivity for medium oils.
【００１４】[0014]
【発明の実施の形態】本発明の変性ゼオライト-βを、
脱アミノ化のために出発材料のゼオライト-βをカ焼す
ること、脱アルミ化のためにゼオライト-βを酸処理
し、その後、高圧下で水熱処理することにより調製す
る。本発明に係る変性ゼオライト-βのＳiＯ 2/Ａl2Ｏ3
の含有比率は高く、固体酸の量を減らしており、そうす
ることで、本発明に係る水素化分解触媒で使用された変
性ゼオライト-βは、中質油に対する優れた選択性を触
媒に提供することができるようになる。BEST MODE FOR CARRYING OUT THE INVENTION The modified zeolite-β of the present invention is
Calcining the starting material zeolite-β for deamination
Treatment of zeolite-β for dealumination
And then hydrothermally treated under high pressure.
You. SiO of modified zeolite-β according to the present invention Two/ AlTwoOThree
Is high and the amount of solid acid is reduced.
As a result, the conversion used in the hydrocracking catalyst according to the present invention is improved.
Zeolite-β has excellent selectivity for medium oils
It can be provided to the medium.
【００１５】本発明に係る触媒で使用されたゼオライト
-βは、上記した本発明のプロセスにより調製した変性
ゼオライト-βであり、これは、無極性炭化水素に対す
る高い吸着性を与え、水のような極性分子には低い吸着
性しか示さないので、通常、疎水性ゼオライト-βまた
は変性超疎水性ゼオライト-βと呼ばれるものである。
本発明に係る触媒で使用される上記のゼオライト-βの
細孔の直径は、＞５×１０-10ｍである。上記のゼオラ
イト-βを調製するプロセスの特徴は、水熱処理がカ焼
による脱アミノ化および酸処理による脱アルミ化の後、
５０〜５００KPaの水蒸気圧下、４００〜９００℃の温
度で、少なくともの０.５時間、好ましくは０.５〜５時
間でなされることである。Zeolite used in the catalyst according to the invention
-β is a modified zeolite-β prepared by the process of the present invention described above, which provides high adsorptivity for non-polar hydrocarbons and only low adsorption for polar molecules such as water, Usually referred to as hydrophobic zeolite-β or modified superhydrophobic zeolite-β.
The pore diameter of the above zeolite-β used in the catalyst according to the invention is> 5 × 10 −10 m. The above process for preparing zeolite-β is characterized by hydrothermal treatment after deamination by calcination and dealumination by acid treatment.
It is carried out at a temperature of 400 to 900 ° C. under a steam pressure of 50 to 500 KPa for at least 0.5 hours, preferably 0.5 to 5 hours.
【００１６】本発明で使用されているゼオライト-βの
水熱処理の目的は、中質油に対する水素化分解触媒の選
択性を増加させるためにゼオライトの構造を変えること
であるが、その方法は、従来技術での、高温下でのカ焼
または酸処理による脱アルミ化の前の水熱処理(この処
理の目的は主として有機アミン鋳型をゼオライトから取
り除くことである)とは別のものである。The purpose of the hydrothermal treatment of the zeolite-β used in the present invention is to change the structure of the zeolite in order to increase the selectivity of the hydrocracking catalyst for medium oils. It is different from the prior art hydrothermal treatment prior to dealumination by calcination or acid treatment at elevated temperatures, the purpose of which is to remove mainly the organic amine template from the zeolite.
【００１７】脱アルミ化の後、本発明に係るゼオライト
-βの酸性部分の量は減少し、その酸性度も０.１〜０.
５mmol/g、好ましくは、０.２〜０.３mmol/gに低下す
る。このために、中質留分を生産するための、本発明の
水素化分解触媒クラッキング活性での要求事項は満たさ
れるが、一方、酸性度の低い部位があるために、第２の
クラッキングの可能性は減少する。他方において、本発
明のゼオライト-βの脱アルミ化の程度は厳しく制御さ
れ、ここで得られた変性ゼオライト-βにおけるＳiＯ2/
Ａl2Ｏ3の含有比は、３０〜９０の範囲となる。After dealumination, the zeolite according to the invention
The amount of the acidic part of -β is reduced and its acidity is also 0.1-0.1.
It drops to 5 mmol / g, preferably 0.2 to 0.3 mmol / g. This satisfies the requirements of the hydrocracking catalyst cracking activity of the present invention for producing a middle distillate, but the possibility of secondary cracking due to the presence of low acidity sites Sex is reduced. On the other hand, the degree of dealumination of the zeolite-β of the present invention is tightly controlled, and the SiO 2 /
The content ratio of Al 2 O 3 is in the range of 30 to 90.
【００１８】本発明の変性超疎水性ゼオライト-βは、
低酸性度を有する変性ゼオライトである。表１に示され
ているように、ゼオライト-Ｙと比較して、本発明の変
性ゼオライト-βの酸性度は低いが、十分なクラッキン
グ活性をもっており、したがって、酸性無定形シリカ-
アルミナと組み合わされて１つの成分となる変性ゼオラ
イト-βから構成される本発明の水素化分解触媒は、高
い酸性度だけでなく中質油に対する高い選択性も示して
いるのである。さらに、この触媒は、比較的高い構造破
壊温度を保持しているために、熱安定性が優れている。
このように、本発明に係る上記のゼオライト-βを、良
好な触媒活性や中質油に対する優れた選択性だけでなく
良好な熱安定性、窒素被毒や炭素蓄積に対する抵抗性を
示す水素化分解触媒を調製するために使えるのである。The modified superhydrophobic zeolite-β of the present invention comprises
Modified zeolite with low acidity. As shown in Table 1, the modified zeolite-β of the present invention has a lower acidity, but has sufficient cracking activity, and therefore has an acidic amorphous silica form, as compared with zeolite-Y.
The hydrocracking catalyst of the present invention, which is composed of modified zeolite-β, which is combined with alumina as one component, shows not only high acidity but also high selectivity to medium oils. Further, the catalyst has excellent thermal stability because it maintains a relatively high structural breakdown temperature.
Thus, the above-mentioned zeolite-β according to the present invention can be hydrogenated not only with good catalytic activity and excellent selectivity to medium oil, but also with good thermal stability, resistance to nitrogen poisoning and carbon accumulation. It can be used to prepare cracking catalysts.
【００１９】[0019]
【表１】 (表１:変性前後のゼオライト-βの
特性) 本発明に係る触媒は、触媒の追加の酸性成分およびキャ
リヤ成分として無定形シリカ-アルミナを使用する。こ
の無定形シリカ-アルミナにおけるＳiＯ2の含有量は１
０〜６０wt%、比表面積は３００〜５００m2/g、細孔容
積は０.７〜１.２ml/g、酸性度は０.３〜０.５mmol/gで
あり、活性キャリヤ成分とゼオライト成分が組合わさっ
て、触媒にクラッキング活性を与え、水素化のための金
属成分を担持する。(Table 1: Properties of zeolite-β before and after denaturation) The catalyst according to the present invention uses amorphous silica-alumina as an additional acidic component and carrier component of the catalyst. The content of SiO 2 in this amorphous silica-alumina is 1
0-60 wt%, specific surface area 300-500 m 2 / g, pore volume 0.7-1.2 ml / g, acidity 0.3-0.5 mmol / g, active carrier component and zeolite component Combine to provide the catalyst with cracking activity and carry the metal component for hydrogenation.
【００２０】本発明に係る触媒は、従来のよく知られた
多様な技術により、ペレット製品や押出し製品のような
形状にできるし、金属を担持するために共沈、混練、混
合、含浸などの方法も使用可能である。本発明に係る触
媒製品の金属成分は、押出し成形や含浸などの方法によ
り調製することが好ましい。特に本発明の触媒は、小細
孔アルミナを硝酸のような酸でペプチゼーションするこ
とで調製された１５〜３０wt%(触媒全重量基準)のバイ
ンダーを加えながら、本発明の５〜４０wt%(触媒全重量
基準)の変性ゼオライト-βを３０〜８０wt%(触媒全重量
基準)の無定形シリカ-アルミナの乾燥粉末と均一に混合
し、その後、その混合物をペーストと混練し、一般的に
は、直径が１.３〜１.８mmの筒形のバーまたはクローバ
形のような特別な形状製品に押し出し成形し、さらにそ
の後、キャリヤを乾燥させ、カ焼により活性化させ、少
なくとも１個の周期表第VIｂ族金属および少なくとも１
個の第VIII族金属などの担持される水素化金属を含む溶
液を、細孔飽和または溶液含浸法により含浸させ、さら
にその後、それらの金属が担持されるキャリヤ棒を乾燥
させ、本発明の触媒を得るために活性化することより調
製される。The catalyst according to the present invention can be formed into a shape such as a pellet product or an extruded product by various well-known conventional techniques. Methods can also be used. The metal component of the catalyst product according to the present invention is preferably prepared by a method such as extrusion or impregnation. In particular, the catalyst of the present invention, while adding 15 to 30 wt% (based on the total weight of the catalyst) binder prepared by peptization of small pore alumina with an acid such as nitric acid, 5 to 40 wt% of the present invention ( The modified zeolite-β (based on the total weight of the catalyst) is uniformly mixed with 30 to 80 wt% (based on the total weight of the catalyst) of dry powder of amorphous silica-alumina, and then the mixture is kneaded with a paste. Extruded into specially shaped products, such as 1.3-1.8 mm diameter cylindrical bar or clover shape, and then drying the carrier, activating by calcining, at least one cycle Table VIb metals and at least one
A solution containing a supported metal hydride, such as a Group VIII metal, is impregnated by pore saturation or solution impregnation, and then the carrier rod on which those metals are supported is dried to form the catalyst of the present invention. It is prepared by activating to obtain
【００２１】本発明の触媒は、触媒の全重量を基準にし
て、１０〜３０wt%の変性ゼオライト-β、２０〜４０wt
%(乾燥アルミナとして計算)の無定形シリカ-アルミナ、
周期表第VIｂ族から選択される２０〜３０wt%(金属酸化
物として計算)の金属(好ましくはＭoおよび/またはＷ)
および第VIII族から選択される４〜８wt%(金属酸化物と
して計算)の金属(好ましくは、Ｃoおよび/またはＮi)を
含んでいることが好ましい。The catalyst of the present invention comprises 10 to 30% by weight of modified zeolite-β, 20 to 40% by weight, based on the total weight of the catalyst.
% (Calculated as dry alumina) amorphous silica-alumina,
20-30% by weight (calculated as metal oxide) of metal (preferably Mo and / or W) selected from group VIb of the periodic table
And preferably from 4 to 8 wt% (calculated as metal oxide) of a metal (preferably Co and / or Ni) selected from Group VIII.
【００２２】水素化分解に使用する本発明の触媒は、特
に２５０〜６００℃、好ましくは、３００〜５５０℃の
留出範囲にある重質炭化水素原料を処理する場合に適し
ているが、上記で述べた特質を有する原料油として、例
えばガス油、真空留出油、脱アスファルト油、触媒クラ
ッキングより発生したリサイクル油、ケツ岩油、コール
タールなどがある。この反応は一般には、水素存在下、
反応圧力が５〜２０MPa、水素とオイルとの比率が１０
０〜５０００、空間速度が０.１〜５.０hrー1、反応温度
が３５０〜４５０℃で起こるようにする。水素化分解プ
ロセスは、原料油からＳとＮのほとんどを除去する段
階、水素化分解を行う場合の厳しい運転状況の緩和がで
きるように、原料油内の多環式アロマティックスを飽和
させるための水素化精製という事前処理段階からなる。
本発明の触媒は、窒素に対して比較的強い抵抗性を示
し、つまり、それにより、使用上での融通性が実現さ
れ、そのために、触媒は単独で使用することができ、重
質炭化水素原料を、単一の触媒を使用して単一段階プロ
セスで処理が可能である。この触媒は比較的高い触媒活
性と中質油に対して高い選択性を示す。The catalyst of the present invention used for hydrocracking is particularly suitable for treating a heavy hydrocarbon raw material having a distillation range of 250 to 600 ° C, preferably 300 to 550 ° C. Examples of the raw material oil having the characteristics described in (1) include gas oil, vacuum distillate oil, deasphalted oil, recycled oil generated from catalytic cracking, ashes rock oil, and coal tar. This reaction is generally carried out in the presence of hydrogen,
The reaction pressure is 5-20MPa, the ratio of hydrogen to oil is 10
0 to 5000, the space velocity is 0.1 to 5.0 hr -1 , and the reaction temperature is 350 to 450 ° C. The hydrocracking process removes most of the S and N from the feedstock, saturating the polycyclic aromatics in the feedstock so that the severe operating conditions of hydrocracking can be reduced. Consists of a pretreatment stage of hydrorefining.
The catalysts of the present invention exhibit a relatively high resistance to nitrogen, i.e., they provide flexibility in use, so that the catalysts can be used alone and heavy hydrocarbons The feed can be processed in a single stage process using a single catalyst. The catalyst exhibits relatively high catalytic activity and high selectivity for medium oils.
【００２３】本発明に係る触媒は、通常のＶＧＯの処理
に使用する際に、その反応が、水素の存在下、圧力が、
好ましくは１０〜２０MPa、水素対オイルの比率が５０
０〜２０００、空間速度が０.５〜２.０hr-1、反応温度
が３７０〜４２０℃で起こるようにする。本発明に係る
触媒は、水素化分解により、中質留出油を生産する際
に、高い触媒活性と中質油に対する選択性を有する。#
３８１２水素化分解触媒との比較のために、本発明の触
媒を、#３８１２の場合と同じ方法、つまり、ほとんど
同じ転化率で、反応温度を３８９℃にして、Daqing VGO
の処理をした場合は、中質油に対する選択率は７５ｗ%
である。本発明の触媒には、運転使用上の融通性があ
り、例えば、製品上の要求事項に合わせた、完全リサイ
クルモードまたは単一経路モードでの運転に使用でき、
操作条件を規制することにより、航空用灯油やディーゼ
ル油を生産上限まで生産することが可能である。さら
に、本発明の触媒は、水素化分解と水素化脱ロウの点に
おいて優れた性能を示し、そのために水素化分解により
得られた製品の品質は優れている。特に、本発明の触媒
を使用することで、低凍結温度のディーゼル油を生産で
き、ディーゼル留分の留出境界点の範囲が広く、これは
ディーゼル油の増産に都合がよい。When the catalyst according to the present invention is used for the treatment of ordinary VGO, the reaction is carried out in the presence of hydrogen and at a pressure of
Preferably 10-20 MPa, hydrogen to oil ratio of 50
0-2000, space velocity 0.5-2.0 hr -1 and reaction temperature 370-420 ° C. INDUSTRIAL APPLICABILITY The catalyst according to the present invention has a high catalytic activity and a selectivity to a medium oil when producing a medium distillate by hydrocracking. #
For comparison with the 3812 hydrocracking catalyst, the catalyst of the present invention was prepared in the same manner as in the case of # 3812, that is, with almost the same conversion, at a reaction temperature of 389 ° C. and Daqing VGO
, The selectivity to medium oil is 75w%
It is. The catalysts of the present invention are versatile in operational use, for example, they can be used in full recycle mode or single-pass mode operation to meet product requirements,
By regulating the operating conditions, it is possible to produce aviation kerosene and diesel oil up to the production limit. Further, the catalyst of the present invention exhibits excellent performance in hydrocracking and hydrodewaxing, and therefore, the quality of the product obtained by hydrocracking is excellent. In particular, by using the catalyst of the present invention, diesel oil having a low freezing temperature can be produced, and the range of the distilling boundary point of the diesel fraction is wide, which is convenient for increasing the production of diesel oil.
【００２４】[0024]
【実施例】本発明を、下記の実施例を参照して、さらに
詳しく説明する。ここで説明した例は、例示が目的であ
って、本発明がこれらの例に限定されるものではない。The present invention will be described in more detail with reference to the following examples. The examples described here are for illustrative purposes, and the invention is not limited to these examples.
【００２５】[実施例１]Ｈ型ゼオライト-β(ＳiＯ2/Ａl
2Ｏ3=２５.１)を、ＳiＯ2/Ａl2Ｏ3の含有比率が４８、
２５℃で水蒸気圧が１２mmＨｇであるときの水分吸着能
が１６.９wt%になるように、０.５Ｎ・ＨＣlで２時間処
理し、さらに、２５℃で水蒸気圧が１２mmＨｇであると
きの水分吸着能が２.６wt%になるように、７５０℃で２
時間水熱処理した。乾燥後、本発明のゼオライト-β(Ｆ
Ａ)を得た。本発明の触媒(ＣＡ)を、２８ｇの小さな細
孔のある擬ベーム石を４０%硝酸の５.７mlを８５mlの蒸
留水に溶解させた希釈硝酸溶液を使ってペプチゼーショ
ンすることにより調製したバインダー(結合剤)を添加し
ながら、２０.７ｇのゼオライトＦＡ、８６.３ｇの大き
な細孔のある無定形シリカ-アルミナ(ＳiＯ2の含有量が
４５wt%、比表面積が３６５m2/g、細孔容積が０.９５６
ml/g、酸性度が０.４０mmol/g)、４７ｇのメタタングス
テート・アンモニウム、４２.１ｇの硝酸ニッケルを均一
に混合し、その結果得られた混合液をペーストに混練
し、さらに、それを直径が１.７mm円筒状細孔のある穴
付きプレートを通して押し出し、その結果得られた押し
出し棒を１１０℃で３時間乾燥した後、５００℃で活性
化させることで、２３.８wt%のＷＯ3、７.４wt%のＮi
Ｏ、１０wt%の疎水性ゼオライト-βからなり、比表面積
が２６４m2/g、細孔容積が０.３２２ml/gである触媒Ｃ
Ａを得た。Example 1 H-type zeolite-β (SiO 2 / Al
2 O 3 = 25.1) when the content ratio of SiO 2 / Al 2 O 3 is 48,
Treat with 0.5N HCl for 2 hours so that the water adsorption capacity at 25 ° C when the water vapor pressure is 12 mmHg is 16.9 wt%, and further, at 25 ° C when the water vapor pressure is 12 mmHg. At 750 ° C so that the capacity becomes 2.6 wt%.
Hydrothermal treatment for hours. After drying, the zeolite-β (F
A) was obtained. Binder prepared by peptizing the catalyst (CA) of the present invention with 28 g of small pored pseudoboehmite using a dilute nitric acid solution of 5.7 ml of 40% nitric acid in 85 ml of distilled water. While adding (binder), 20.7 g of zeolite FA, 86.3 g of large pore amorphous silica-alumina (SiO 2 content 45 wt%, specific surface area 365 m 2 / g, fine pore 0.956 volume
ml / g, acidity 0.40 mmol / g), 47 g of metatungstate ammonium and 42.1 g of nickel nitrate are uniformly mixed, and the resulting mixture is kneaded into a paste. Was extruded through a perforated plate with 1.7 mm diameter cylindrical pores, and the resulting extruded rod was dried at 110 ° C. for 3 hours and then activated at 500 ° C. to obtain 23.8 wt% WO. 3 , 7.4 wt% Ni
O, a catalyst C comprising 10 wt% of hydrophobic zeolite-β, having a specific surface area of 264 m 2 / g and a pore volume of 0.322 ml / g
A was obtained.
【００２６】[実施例２]Ｈ型ゼオライト-β(ＳiＯ2/Ａl
2Ｏ3=２５.１)を、ＳiＯ2/Ａl2Ｏ3の含有比率が４８、
２５℃で水蒸気圧が１２mmＨｇであるときの水分吸着能
が１６.９wt%になるように、０.５Ｎ・ＨＣlで２時間処
理し、さらに、２５℃で水蒸気圧が１２mmＨｇであると
きの水分吸着能が７.３wt%になるように、５５０℃で２
時間水熱処理し、その後、乾燥して本発明のゼオライト
-β(ＦＢ)を得た。そのゼオライトＦＢの４１.６ｇ、１
１６.４ｇの大きな細孔のある無定形シリカ-アルミナ
(ＳiＯ2の含有量が２５wt%、比表面積が３３２m2/g、細
孔容積が０.９２２ml/g、酸性度が０.３４mmol/g)を均
一に混合し、その後、２８ｇの小さな細孔のある擬ベー
ム石を５.７mlの４０%硝酸を８５mlの蒸留水に溶解させ
た希釈硝酸溶液でペプチゼーションさせて調製したバイ
ンダーを添加し、さらにその後、混合液をペーストと混
練させ、それを直径が１.７mmの円筒状の細孔のある穴
付きプレートを通して押し出し、その押し出された棒を
１１０℃で乾燥し、５００℃で３時間活性化させて、３
９ｇの酸化モリブデン、４１ｇの硝酸ニッケル、８５%
のＨ3ＰＯ4から調製した溶液を含浸させてキャリヤを作
製した。金属が担持されるそのキャリヤを、その後５０
０℃で３時間活性化させて、２３.４wt%のＭＯ3、６.７
wt%のＮiＯ、１５wt%の疎水性ゼオライト-βからなり、
比表面積が２６８m2/g、細孔容積が０.３２９ml/gであ
る本発明の触媒(ＣＢ)を得た。Example 2 H-type zeolite-β (SiO 2 / Al
2 O 3 = 25.1) when the content ratio of SiO 2 / Al 2 O 3 is 48,
Treat with 0.5N HCl for 2 hours so that the water adsorption capacity at 25 ° C when the water vapor pressure is 12 mmHg is 16.9 wt%, and further, at 25 ° C when the water vapor pressure is 12 mmHg. 2 at 550 ° C so that the capacity becomes 7.3 wt%.
Hydrothermal treatment for a period of time and then dry to form the zeolite of the present invention.
-β (FB) was obtained. 41.6 g of the zeolite FB, 1
16.4g of large pore amorphous silica-alumina
(SiO 2 content: 25 wt%, specific surface area: 332 m 2 / g, pore volume: 0.922 ml / g, acidity: 0.34 mmol / g) A binder prepared by peptizing simulated boehmite with dilute nitric acid solution of 5.7 ml of 40% nitric acid in 85 ml of distilled water is added, and then the mixture is kneaded with the paste. Extruded through a 1.7 mm diameter cylindrical perforated plate with pores, the extruded rod was dried at 110 ° C., activated at 500 ° C. for 3 hours,
9 g molybdenum oxide, 41 g nickel nitrate, 85%
A carrier prepared by impregnating a solution prepared from H 3 PO 4 . The carrier on which the metal is carried is then
Activated at 0 ° C. for 3 hours, 23.4 wt% MO 3 , 6.7
consisting of wt% NiO, 15 wt% hydrophobic zeolite-β,
A catalyst (CB) of the present invention having a specific surface area of 268 m 2 / g and a pore volume of 0.329 ml / g was obtained.
【００２７】[実施例３]実施例１で得たゼオライトＦＡ
の６２.４ｇ、１０６.３ｇの大きい細孔の無定形シリカ
-アルミナ(ＳiＯ2の含有量が３５wt%、比表面積が３９
６m2/g、細孔容積が０.９９６ml/g、酸性度が０.３４mm
ol/g)を均一に混合し、４０%硝酸の５.７mｌを８５mlの
蒸留水に溶解した希釈硝酸溶液でペプチゼーションする
ことで調製したバインダーを添加し、その結果得られた
混合液をペーストと混練させ、その後、直径が１.７mm
の円筒状細孔のある穴あきプレートを通して押し出し、
その結果得られた押し出し棒を１１０℃で乾燥させ、４
７ｇのメタタングステート・アンモニアと４２.１ｇの硝
酸ニッケルにより調製した溶液を含浸させたキャリヤを
得、さらに、５００℃で３時間活性化させて、２４.５w
t%のＷＯ3、６.８wt%のＮiＯ、３０wt%の疎水性ゼオラ
イト-βからなり、比表面積が２７８m2/g、細孔容積が
０.３１８ml/gである本発明の触媒(ＣＣ)を得た。Example 3 Zeolite FA obtained in Example 1
62.4g, 106.3g large pore amorphous silica
-Alumina (SiO 2 content 35 wt%, specific surface area 39
6m 2 / g, pore volume 0.996ml / g, acidity 0.34mm
ol / g), and a binder prepared by peptizing 5.7 ml of 40% nitric acid with a diluted nitric acid solution dissolved in 85 ml of distilled water is added. The resulting mixed solution is pasteurized. And then, 1.7mm in diameter
Extruded through a perforated plate with cylindrical pores of
The resulting extruded rod was dried at 110 ° C.
A carrier impregnated with a solution prepared with 7 g of metatungstate ammonia and 42.1 g of nickel nitrate was obtained and further activated at 500 ° C. for 3 hours to give 24.5 w
The catalyst of the present invention (CC) comprising t% WO 3 , 6.8 wt% NiO, 30 wt% hydrophobic zeolite-β, having a specific surface area of 278 m 2 / g and a pore volume of 0.318 ml / g (CC) I got
【００２８】[実施例４=比較例１]対照触媒を、本発明
での疎水性ゼオライト-βの代わりに、上記したような
ＵＳＹなどの超疎水性のゼオライトＹ(酸性度が１.１mm
ol/g)を使用した以外は、実施例１と同じ方法で調製し
た。この対照触媒は、２２.３wt%のＭoＯ3、７.２wt%の
ＮiＯ、１５wt%のゼオライトＹからなり、その比表面積
は３０１m2/g、細孔容積は０.３８６ml/gで、対照触媒
(ＹＣ)とした。[Example 4 = Comparative Example 1] A superhydrophobic zeolite Y such as USY described above (acidity of 1.1 mm) was used instead of the hydrophobic zeolite-β in the present invention.
ol / g), except that ol / g) was used. This control catalyst was composed of 22.3 wt% MoO 3 , 7.2 wt% NiO and 15 wt% zeolite Y, having a specific surface area of 301 m 2 / g and a pore volume of 0.386 ml / g.
(YC).
【００２９】[実施例５]実施例１〜４での触媒を、圧力
が１４.７MPa、水素対オイル比率が１２００、空間速度
が１.５hrー1の条件で、２００ml固定床リアクタを使用
して評価した。評価の前に、触媒を硫化させた。表２
は、評価した原料オイルの特性を示したものである。１
段直列プロセスの場合、水素化分解触媒を第２のリアク
タに充填して、水素化精製触媒を第１のリアクタに充填
した。その結果、第２のリアクタに入る精製オイルの窒
素含有量が１０μｇ/g以下になった。表３は、１段直列
プロセスの評価結果を示したものである。表４は、完全
リサイクル運転の１段直列プロセスの評価結果を示し、
そして表５にはその処理製品の特性を示す。本発明の触
媒は、その酸性点特性や窒素に対する強い抵抗性のため
に、単一触媒を使用した単一段階プロセスで、原料を処
理できる。表６は、単一触媒と対照触媒#３８１２を使
用した単一段階プロセスにより、Daqing VGOを処理した
場合の評価結果である。Example 5 The catalysts of Examples 1 to 4 were used at a pressure of 14.7 MPa, a hydrogen to oil ratio of 1200, and a space velocity of 1.5 hr -1 using a 200 ml fixed bed reactor. Was evaluated. Prior to evaluation, the catalyst was sulfided. Table 2
Shows the characteristics of the evaluated raw oil. 1
In the case of a stage-serial process, the hydrocracking catalyst was charged into the second reactor, and the hydrorefining catalyst was charged into the first reactor. As a result, the nitrogen content of the refined oil entering the second reactor became 10 μg / g or less. Table 3 shows the evaluation results of the one-stage serial process. Table 4 shows the evaluation results of the one-stage in-line process of the complete recycle operation,
Table 5 shows the characteristics of the processed product. The catalysts of the present invention can process feedstock in a single-stage process using a single catalyst due to its acidic point properties and strong resistance to nitrogen. Table 6 shows the evaluation results when Daqing VGO was treated by a single-stage process using a single catalyst and control catalyst # 3812.
【００３０】[0030]
【表２】 (表２:原料オイルの特性) [Table 2] (Table 2: Characteristics of raw oil)
【００３１】[0031]
【表３】 (表３:１段直列プロセス単一処理の評
価結果) [Table 3] (Table 3: Evaluation results of single-stage serial process single processing)
【００３２】[0032]
【表４】 (表４:１段直列プロセス完全リサイクル処
理の評価結果) [Table 4] (Evaluation result of complete recycle processing of one-stage serial process)
【００３３】[0033]
【表５】 (表５:水素化分解製品の特性) [Table 5] (Table 5: Characteristics of hydrocracking products)
【００３４】[0034]
【表６】 (表６:単一触媒、１段プロセス処理の結果
評価) *注:触媒#３８１２のデータの出所は「中国精製技術」 pp.511 本発明は、実施例により詳細に説明されているが、本発
明の精神を逸脱せづに多様な修正と改良が可能であるこ
とは当業者に理解される。したがって、これらの修正と
改良がすべて本発明の範囲内であることは明白である。[Table 6: Evaluation of single catalyst, one-stage process treatment result] * Note: Source of data for catalyst # 3812 is "China Refining Technology" pp.511 Although the present invention has been described in detail with reference to examples, various modifications and improvements can be made without departing from the spirit of the present invention. Is understood by those skilled in the art. It is therefore evident that all of these modifications and improvements are within the scope of the present invention.
【００３５】[0035]
【発明の効果】本発明の触媒は、運転使用上の融通性が
あり、操作条件を規制することにより航空灯油やディー
ゼル油を生産上限まで生産することが可能である。さら
に、本発明の触媒は、水素化分解と水素化脱ロウの点に
おいて優れた性能を示し、そのために水素化分解により
優れた品質の製品が得られる。特に低凍結温度のディー
ゼル油を生産でき、ディーゼル留分の留出境界点の範囲
が広く、ディーゼル油の増産に好適である。Industrial Applicability The catalyst of the present invention has versatility in operation and use, and is capable of producing aviation kerosene and diesel oil up to the upper limit of production by regulating the operation conditions. In addition, the catalysts of the present invention exhibit excellent performance in hydrocracking and hydrodewaxing, so that products of excellent quality are obtained by hydrocracking. In particular, diesel oil with a low freezing temperature can be produced, and the range of the distilling boundary point of the diesel fraction is wide, which is suitable for increasing the production of diesel oil.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ１０Ｌ 1/00 Ｃ１０Ｌ 1/00 Ｆ０２Ｂ 3/06 Ｆ０２Ｂ 3/06 Ａ (72)発明者 張 奎喜 中國遼寧省撫順市望花區丹東路31號 (72)発明者 侯 玉鐸 中國遼寧省撫順市望花區丹東路31號 (72)発明者 ▲トン▼ 明海 中國遼寧省撫順市望花區丹東路31號──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI C10L 1/00 C10L 1/00 F02B 3/06 F02B 3/06 A (72) Inventor Zhang Keiki Wanghua District, Fushun City, Liaoning Province, China No. 31 Dandong Road (72) Inventor Hou Yudaku 31 No. 31 Dandong Road, Wanhua District, Fushun City, Liaoning Province, China (72) Inventor
Claims (9)
を含み、低酸性度の変性超疎水性ゼオライト-β、水素
化成分としての、金属酸化物の形での、少なくとも１個
の担持される周期表第VIｂ族金属および少なくとも１個
の担持される第VIII族金属からなり、前記ゼオライト-
βにおけるＳiＯ2/Ａl2Ｏ3の含有比率が３０〜９０であ
り、ピリジン吸着ＩＲ法で測定した酸性度が０.１〜０.
５mmol/g、温度２５℃で水蒸気圧が１２mmＨｇ以下のと
きの水分吸着能が１０%以下である、中質留出油を生産
するための水素化分解触媒。1. Low acidity modified superhydrophobic zeolite-β comprising amorphous silica-alumina as acidic component, at least one supported period in the form of a metal oxide as hydrogenating component. The zeolite comprises a Group VIb metal and at least one supported Group VIII metal.
The content ratio of SiO 2 / Al 2 O 3 in β is 30 to 90, and the acidity measured by the pyridine adsorption IR method is 0.1 to 0.1.
A hydrocracking catalyst for producing a medium distillate, which has a water adsorption capacity of 10% or less when 5 mmol / g, a temperature of 25 ° C. and a steam pressure is 12 mmHg or less.
イト-β、１０〜５０wt%の無定形シリカ-アルミナ、１
５〜３０wt%のアルミナ、１０〜４０wt%の少なくとも１
個の第VIｂ族金属酸化物、少なくとも１個の１〜１０wt
%の第VIII族金属酸化物からなることを特徴とする請求
項１記載の触媒。2. 5 to 40% by weight of the modified superhydrophobic zeolite-β, 10 to 50% by weight of amorphous silica-alumina,
5-30 wt% alumina, 10-40 wt% at least 1
VIb metal oxides, at least one 1-10 wt
2. The catalyst of claim 1, wherein the catalyst comprises about 10% Group VIII metal oxide.
細孔容積が０.３〜０.４ml/g、ピリジン吸着ＩＲ法によ
り測定した酸性度が０.３〜０.５mmol/gであることを特
徴とする請求項１記載の触媒。3. The catalyst has a specific surface area of 200 to 300 m 2 / g,
2. The catalyst according to claim 1, wherein the catalyst has a pore volume of 0.3 to 0.4 ml / g and an acidity of 0.3 to 0.5 mmol / g measured by a pyridine adsorption IR method.
焼による脱アミノ化および酸処理による脱アルミ化のス
テップの後、高圧下で水熱処理することにより、Ｈ-型
ゼオライト-βから調製されることを特徴とする請求項
１記載の触媒。4. The modified superhydrophobic zeolite-β is prepared from H-type zeolite-β by deamination by calcination and dealumination by acid treatment, followed by hydrothermal treatment under high pressure. The catalyst according to claim 1, wherein the catalyst is used.
気圧下で、温度４００〜９００℃で少なくとも０.５時
間、好ましくは０.５〜５時間実施されることを特徴と
する請求項４記載の触媒。5. The method according to claim 4, wherein the hydrothermal treatment is carried out at a temperature of 400 to 900 ° C. for at least 0.5 hours, preferably for 0.5 to 5 hours, under a vapor pressure of 50 to 500 KPa. Catalyst.
から選択され、その含有量が、金属酸化物の形で、触媒
の全重量基準で１０〜４０wt%であることを特徴とする
請求項２記載の触媒。6. The group VIb metal is Mo and / or W
3. The catalyst according to claim 2, wherein the content is from 10 to 40% by weight, based on the total weight of the catalyst, in the form of metal oxides.
から選択され、その含有量が、金属酸化物の形で、触媒
の全重量基準で１〜１０wt%であることを特徴とする請
求項２記載の触媒。7. The method of claim 7, wherein said Group VIII metal is Co and / or Ni.
3. The catalyst according to claim 2, wherein the content is from 1 to 10% by weight, based on the total weight of the catalyst, in the form of metal oxides.
ト-β、２０〜４０wt%の無定形シリカ-アルミナ、１５
〜３０wt%のアルミナ、２０〜３０wt%の第VIｂ族金属酸
化物、４〜８wt%の第VIII族金属酸化物からなる請求項
２記載の触媒。8. 10-30% by weight of modified superhydrophobic zeolite-β, 20-40% by weight of amorphous silica-alumina, 15% by weight
3. A catalyst as claimed in claim 2, comprising -30% by weight of alumina, 20-30% by weight of Group VIb metal oxide and 4-8% by weight of Group VIII metal oxide.
有量が１０〜６０%、比表面積が３００〜５００m2/g、
細孔容積が０.７〜１.２ml/g、ピリジン吸着ＩＲ法で測
定した酸性度が０.３〜０.５mmol/gであることを特徴と
する請求項２記載の触媒。9. The amorphous silica-alumina has a SiO 2 content of 10 to 60%, a specific surface area of 300 to 500 m 2 / g,
3. The catalyst according to claim 2, wherein the pore volume is 0.7 to 1.2 ml / g and the acidity measured by pyridine adsorption IR method is 0.3 to 0.5 mmol / g.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97116403A CN1054153C (en) | 1997-09-10 | 1997-09-10 | Hydrocracking catalyst for producing intermediate fraction oil |
| CN97116403-7 | 1997-09-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11156198A true JPH11156198A (en) | 1999-06-15 |
| JP3688476B2 JP3688476B2 (en) | 2005-08-31 |
Family
ID=5173824
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25664798A Expired - Lifetime JP3688476B2 (en) | 1997-09-10 | 1998-09-10 | Hydrocracking catalyst for medium distillate oil production |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP3688476B2 (en) |
| KR (1) | KR100376563B1 (en) |
| CN (1) | CN1054153C (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003039747A3 (en) * | 2001-11-07 | 2004-02-12 | Uop Llc | Middle distillate selective hydrocracking process |
| KR100419288B1 (en) * | 2001-06-22 | 2004-02-19 | 인천정유 주식회사 | Method for preparing catalysts for dearomatization in distillate |
| US6835369B2 (en) * | 1998-06-29 | 2004-12-28 | California Institute Of Technology | Molecular sieve CIT-6 |
| US7169291B1 (en) | 2003-12-31 | 2007-01-30 | Uop Llc | Selective hydrocracking process using beta zeolite |
| JP2010215433A (en) * | 2009-03-13 | 2010-09-30 | Idemitsu Kosan Co Ltd | Beta-zeolite and hydrogenolysis catalyst |
| JP2010215434A (en) * | 2009-03-13 | 2010-09-30 | Idemitsu Kosan Co Ltd | Method for manufacturing beta-zeolite and method for manufacturing hydrogenolysis catalyst |
| JP2014147931A (en) * | 2000-04-20 | 2014-08-21 | Basf Corp | Catalyst, catalyst support and process for hydrogenation, hydroisomerization, hydrocracking and/or hydrodesulfurization |
| JP2016539074A (en) * | 2013-11-26 | 2016-12-15 | チャイナ ペトロレウム アンド ケミカル コーポレーションChina Petroleum & Chemical Corporation | β molecular sieve, process for producing the same, and hydrogenation catalyst containing the same |
| JP2021080132A (en) * | 2019-11-19 | 2021-05-27 | 東ソー株式会社 | Hydrophobic zeolite and method for producing the same |
| CN112844465A (en) * | 2021-01-25 | 2021-05-28 | 中国石油天然气股份有限公司 | Hydrocracking catalyst and application thereof |
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| CN1108356C (en) * | 2000-10-26 | 2003-05-14 | 中国石油化工股份有限公司 | High-activity high-or medium-oilness hydrocracking catalyst and its preparing process |
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| CN1331604C (en) * | 2004-06-21 | 2007-08-15 | 中国石油化工股份有限公司 | Hydrogenation catalyst carrier and production thereof |
| CN100340639C (en) * | 2004-10-29 | 2007-10-03 | 中国石油化工股份有限公司 | Hydrocracking catalyst containing IIB metal oxide and uses |
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| CN1986747B (en) * | 2005-12-23 | 2011-06-15 | 中国石油化工股份有限公司 | Diesel oil fraction hydrogenating modification process |
| KR100968385B1 (en) * | 2008-10-01 | 2010-07-09 | 한국화학연구원 | Method for Preparing Ni-Mo/Silica-Alumina Catalyst and Method for Producing Middle Distillate Using Said Catalyst |
| US8394255B2 (en) * | 2008-12-31 | 2013-03-12 | Exxonmobil Research And Engineering Company | Integrated hydrocracking and dewaxing of hydrocarbons |
| CN102773117A (en) * | 2012-08-21 | 2012-11-14 | 中国海洋石油总公司 | Medium-oil-type hydrocracking catalyst and preparation method thereof |
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Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1149307A (en) * | 1979-11-13 | 1983-07-05 | Union Carbide Corporation | Midbarrel hydrocracking |
| US4820402A (en) * | 1982-05-18 | 1989-04-11 | Mobil Oil Corporation | Hydrocracking process with improved distillate selectivity with high silica large pore zeolites |
| US4719474A (en) * | 1985-07-19 | 1988-01-12 | Rudolf Hell Gmbh | Apparatus for imaging text and graphics on photosensitive material |
| FI885685A (en) * | 1987-12-08 | 1989-06-09 | Uop Inc | NY, FOERBAETTRAD KATALYSATOR FOER HYDROKRACKNING AV TUNGOLJAMELLANDESTILLAT SAMT FOERFARANDE FOER UTNYTTJANDE DAERAV. |
-
1997
- 1997-09-10 CN CN97116403A patent/CN1054153C/en not_active Expired - Lifetime
-
1998
- 1998-09-09 KR KR10-1998-0037230A patent/KR100376563B1/en not_active IP Right Cessation
- 1998-09-10 JP JP25664798A patent/JP3688476B2/en not_active Expired - Lifetime
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6835369B2 (en) * | 1998-06-29 | 2004-12-28 | California Institute Of Technology | Molecular sieve CIT-6 |
| JP2014147931A (en) * | 2000-04-20 | 2014-08-21 | Basf Corp | Catalyst, catalyst support and process for hydrogenation, hydroisomerization, hydrocracking and/or hydrodesulfurization |
| KR100419288B1 (en) * | 2001-06-22 | 2004-02-19 | 인천정유 주식회사 | Method for preparing catalysts for dearomatization in distillate |
| WO2003039747A3 (en) * | 2001-11-07 | 2004-02-12 | Uop Llc | Middle distillate selective hydrocracking process |
| US7048845B2 (en) | 2001-11-07 | 2006-05-23 | Uop Llc | Middle distillate selective hydrocracking process |
| US7169291B1 (en) | 2003-12-31 | 2007-01-30 | Uop Llc | Selective hydrocracking process using beta zeolite |
| US7462276B2 (en) | 2003-12-31 | 2008-12-09 | Uop Llc | Two stage hydrocracking process using beta zeolite for production of LPG and distillate hydrocarbons |
| JP2010215433A (en) * | 2009-03-13 | 2010-09-30 | Idemitsu Kosan Co Ltd | Beta-zeolite and hydrogenolysis catalyst |
| JP2010215434A (en) * | 2009-03-13 | 2010-09-30 | Idemitsu Kosan Co Ltd | Method for manufacturing beta-zeolite and method for manufacturing hydrogenolysis catalyst |
| JP2016539074A (en) * | 2013-11-26 | 2016-12-15 | チャイナ ペトロレウム アンド ケミカル コーポレーションChina Petroleum & Chemical Corporation | β molecular sieve, process for producing the same, and hydrogenation catalyst containing the same |
| JP2021080132A (en) * | 2019-11-19 | 2021-05-27 | 東ソー株式会社 | Hydrophobic zeolite and method for producing the same |
| CN112844465A (en) * | 2021-01-25 | 2021-05-28 | 中国石油天然气股份有限公司 | Hydrocracking catalyst and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1210881A (en) | 1999-03-17 |
| CN1054153C (en) | 2000-07-05 |
| JP3688476B2 (en) | 2005-08-31 |
| KR19990029665A (en) | 1999-04-26 |
| KR100376563B1 (en) | 2003-05-17 |
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