JP5628027B2 - Fluid catalytic cracking catalyst of hydrocarbon oil and fluid catalytic cracking method of hydrocarbon oil using the same - Google Patents
Fluid catalytic cracking catalyst of hydrocarbon oil and fluid catalytic cracking method of hydrocarbon oil using the same Download PDFInfo
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- JP5628027B2 JP5628027B2 JP2010514560A JP2010514560A JP5628027B2 JP 5628027 B2 JP5628027 B2 JP 5628027B2 JP 2010514560 A JP2010514560 A JP 2010514560A JP 2010514560 A JP2010514560 A JP 2010514560A JP 5628027 B2 JP5628027 B2 JP 5628027B2
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- 239000003054 catalyst Substances 0.000 title claims description 388
- 238000004231 fluid catalytic cracking Methods 0.000 title claims description 133
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- 229930195733 hydrocarbon Natural products 0.000 title claims description 48
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 48
- 238000000034 method Methods 0.000 title claims description 18
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 64
- 229910021536 Zeolite Inorganic materials 0.000 claims description 48
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 48
- 239000010457 zeolite Substances 0.000 claims description 48
- 239000003502 gasoline Substances 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 239000000377 silicon dioxide Substances 0.000 claims description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- 229910052782 aluminium Inorganic materials 0.000 claims description 28
- -1 aluminum compound Chemical class 0.000 claims description 27
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- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 18
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 14
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- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
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- 230000000052 comparative effect Effects 0.000 description 14
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- 239000005995 Aluminium silicate Substances 0.000 description 12
- 235000012211 aluminium silicate Nutrition 0.000 description 12
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 12
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 12
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- 238000009835 boiling Methods 0.000 description 6
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- 239000000843 powder Substances 0.000 description 5
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- 150000001875 compounds Chemical class 0.000 description 4
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- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
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- 230000000996 additive effect Effects 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
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- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
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- 238000004438 BET method Methods 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910001680 bayerite Inorganic materials 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical class Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000002909 rare earth metal compounds Chemical class 0.000 description 1
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- 230000001172 regenerating effect Effects 0.000 description 1
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- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- 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
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- 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
- B01J29/80—Mixtures of different zeolites
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Description
本発明は、ガソリン及び軽油留分が高収率で得られると共に、高ボトム分解能、かつ、低コーク収率である炭化水素油の流動接触分解触媒及びそれを用いた炭化水素油の流動接触分解方法に関する。 The present invention provides a fluid catalytic cracking catalyst for hydrocarbon oils having a high bottom resolution and a low coke yield, as well as fluid catalytic cracking of hydrocarbon oils using the same, in which gasoline and light oil fractions are obtained in high yield. Regarding the method.
従来、炭化水素油の流動接触分解において、ガソリンを高収率で得ると共に、コークの収率を低くするために、結合剤としてシリカゾル等のシリカ系バインダーを用いた流動接触分解触媒が開発されている（例えば、特許文献１参照）。しかしながら、シリカ系バインダーを用いた流動接触分解触媒においては、より高いボトム分解性が求められていた。 In the past, fluidized catalytic cracking of hydrocarbon oils has been developed in order to obtain gasoline in high yield and lower the yield of coke, and fluid catalytic cracking catalysts using silica-based binders such as silica sol as binders have been developed. (For example, refer to Patent Document 1). However, a fluid catalytic cracking catalyst using a silica-based binder has been required to have higher bottom decomposability.
また、ガソリン及び灯軽油留分（灯油留分及び軽油留分。Light Cycle Oil。以下、「ＬＣＯ」ともいう）を高収率で得ると共に、ボトムの分解能を高くする、すなわち、重質留分（Heavy Cycle Oil。以下、「ＨＣＯ」ともいう）を低収率にするために、結合剤として塩基性塩化アルミニウム等のアルミナ化合物バインダーを用いた流動接触分解触媒が開発されている（例えば、特許文献２参照）。しかしながら、アルミナ化合物バインダーを用いた流動接触分解触媒においては、コークをより低収率にすることが求められていた。 Also, gasoline and kerosene oil fraction (kerosene fraction and light oil fraction; Light Cycle Oil; hereinafter also referred to as “LCO”) is obtained in a high yield and the bottom resolution is increased, that is, the heavy fraction In order to reduce the yield of heavy cycle oil (hereinafter also referred to as “HCO”), fluid catalytic cracking catalysts using an alumina compound binder such as basic aluminum chloride as a binder have been developed (for example, patents). Reference 2). However, in a fluid catalytic cracking catalyst using an alumina compound binder, it has been required to make coke a lower yield.
ここで、流動接触分解装置（実装置）においては、得られる生成油が求める組成（例えば、「ガソリンを多く」、「灯軽油留分を多く」等）になるように、流動接触分解触媒を切り替えて使用していた。また、原料油が替わると、得られる生成油の組成が変わるため、得られる生成油が求める組成になるように、流動接触分解触媒を切り替えていた。その際には、（１）シリカ系バインダーを含む触媒から他のシリカ系バインダーを含む触媒に切り替える場合、（２）アルミニウム化合物バインダーを含む触媒から他のアルミニウム化合物バインダーを含む触媒に切り替える場合、（３）シリカ系バインダーを含む触媒からアルミニウム化合物バインダーを含む触媒へ切り替える場合、（４）アルミニウム化合物バインダーを含む触媒からシリカ系バインダーを含む触媒へ切り替える場合がある。ここで、触媒を切り替える場合には、まず装置内の第１の触媒の一部を取り出し、次にその取り出し量と同じ量の第２の触媒を装置内へ投入する。この場合、流動接触分解装置内では、第１の触媒と第２の触媒との混合比（質量比）が徐々に変化して、最終的には装置内が第１の触媒から第２の触媒に置き替えていた。その際には、触媒活性、転化率、ガソリン収率等の変化はあったが、新たに添加した触媒に起因するもの、又は、装置の運転条件に起因するものであると考えられていた。 Here, in the fluid catalytic cracking device (actual device), the fluid catalytic cracking catalyst is used so that the resulting product oil has the desired composition (for example, “more gasoline”, “more kerosene fraction”, etc.). I was switching and using it. Moreover, since the composition of the resulting product oil changes when the raw material oil is changed, the fluid catalytic cracking catalyst has been switched so as to obtain the desired composition of the resulting product oil. In that case, (1) When switching from a catalyst containing a silica-based binder to a catalyst containing another silica-based binder, (2) When switching from a catalyst containing an aluminum compound binder to a catalyst containing another aluminum compound binder, 3) When switching from a catalyst containing a silica-based binder to a catalyst containing an aluminum compound binder, (4) sometimes switching from a catalyst containing an aluminum compound binder to a catalyst containing a silica-based binder. Here, when switching the catalyst, first, a part of the first catalyst in the apparatus is taken out, and then the second catalyst having the same amount as that taken out is put into the apparatus. In this case, in the fluid catalytic cracking apparatus, the mixing ratio (mass ratio) of the first catalyst and the second catalyst gradually changes, and finally the inside of the apparatus is changed from the first catalyst to the second catalyst. It was replaced with. At that time, there were changes in catalyst activity, conversion rate, gasoline yield, etc., but it was thought to be due to newly added catalyst or due to operating conditions of the apparatus.
また、流動接触分解触媒に添加されるアディティブ触媒（添加触媒）があるが、これらは流動接触分解触媒の性能（例えば、脱ＮＯｘ、脱ＳＯｘ、耐メタル性、オクタン価向上、ボトム分解能など）を補うものであり、ガソリン及び軽油留分を高収率で得ると共に、高ボトム分解能、かつ、低コーク収率を満たすものではなかった。 In addition, there are additive catalysts (added catalysts) that are added to the fluid catalytic cracking catalyst. These supplement the fluid catalytic cracking catalyst performance (eg, NOx removal, SOx removal, metal resistance, octane number improvement, bottom resolution, etc.). However, the gasoline and diesel oil fractions were obtained in high yields, and did not satisfy high bottom resolution and low coke yields.
しかしながら、従来の流動接触分解触媒では、高ガソリン収率、高軽油留分収率、低コーク収率、及び、高ボトム分解率のいずれをも満たす触媒が開発されていないという問題があった。 However, the conventional fluid catalytic cracking catalyst has a problem that a catalyst satisfying any of high gasoline yield, high light oil fraction yield, low coke yield and high bottom cracking rate has not been developed.
本発明はかかる事情に鑑みてなされたもので、ガソリン及び軽油留分が高収率で得られると共に、高ボトム分解、及び、低コーク収率である炭化水素油の流動接触分解触媒及びそれを用いた炭化水素油の流動接触分解方法を提供することを目的とする。 The present invention has been made in view of such circumstances, and a gasoline and gas oil fraction can be obtained in a high yield, a high bottom cracking, and a fluid catalytic cracking catalyst for hydrocarbon oil having a low coke yield, and It aims at providing the fluid catalytic cracking method of the used hydrocarbon oil.
すなわち、本発明の要旨は、以下の通りである。
［１］ゼオライト及び結合剤として１０〜３０質量％のシリカ系バインダーを含む触媒組成物Ａと、ゼオライト及び結合剤として１０〜３０質量％のアルミニウム化合物バインダーを含む触媒組成物Ｂとを、触媒組成物Ａの質量をＷAとし、触媒組成物Ｂの質量をＷBとして、質量比（ＷA：ＷB）が１０：９０〜９０：１０の範囲内の任意の割合で混合したことを特徴とする炭化水素油の流動接触分解触媒。
［２］前記触媒組成物Ａ及び前記触媒組成物Ｂは、下記式（１）に示すＫ値（それぞれのＫ値は「ＫA」、「ＫB」で表す）が１以上であることを特徴とする［１］の炭化水素油の流動接触分解触媒。That is, the gist of the present invention is as follows.
[1] A catalyst composition comprising a catalyst composition A containing 10-30% by mass of a silica-based binder as a zeolite and a binder, and a catalyst composition B containing 10-30% by mass of an aluminum compound binder as a zeolite and a binder. the mass of the object a and W a, the weight of the catalyst composition B as W B, the mass ratio (W a: W B) is 10: 90 to 90: characterized in that a mixture in any ratio within 1:10 A fluid catalytic cracking catalyst for hydrocarbon oils.
[2] The catalyst composition A and the catalyst composition B have a K value represented by the following formula (1) (each K value is represented by “K A ” and “K B ”) of 1 or more. The fluid catalytic cracking catalyst for hydrocarbon oils according to [1].
Ｋ＝転化率／（１００−転化率）・・・（１）
なお、転化率は、下記式（２）で示される。K = conversion / (100-conversion) (1)
In addition, a conversion rate is shown by following formula (2).
転化率（質量％）＝（ａ−ｂ）／ａ×１００・・・（２）
ここで、ａは原料油の質量、ｂは灯軽油留分及び重質留分の合計の質量である。
［３］前記触媒組成物Ａ及び前記触媒組成物ＢのＫ値は下記式（３）に示す関係にあることを特徴とする［１］又は［２］の炭化水素油の流動接触分解触媒。Conversion (mass%) = (ab) / a × 100 (2)
Here, a is the mass of the raw material oil, and b is the total mass of the kerosene oil fraction and the heavy fraction.
[3] The fluid catalytic cracking catalyst for hydrocarbon oils according to [1] or [2], wherein the K values of the catalyst composition A and the catalyst composition B have a relationship represented by the following formula (3).
ＫA：ＫB＝１：０．５〜１：１．５・・・（３）
［４］前記流動接触分解触媒のＫ値（Ｋm）が、前記触媒組成物ＡのＫ値（ＫA）及び前記触媒組成物ＢのＫ値（ＫB）よりも高いことを特徴とする［１］〜［３］のいずれかの炭化水素油の流動接触分解触媒。
［５］流動接触分解触媒のガソリン収率Ｇmが、触媒組成物Ａのガソリン収率ＧA及び触媒組成物Ｂのガソリン収率ＧBよりも高いことを特徴とする［１］〜［４］のいずれかの炭化水素油の流動接触分解触媒。
［６］前記シリカ系バインダーがシリカゾル、水ガラス、及び、ケイ酸液のいずれか１又は２以上であることを特徴とする［１］〜［５］のいずれかの炭化水素油の流動接触分解触媒。
［７］前記アルミニウム化合物バインダーが、下記（ａ）〜（ｃ）からなる群から選ばれる少なくとも１種であることを特徴とする［１］〜［６］のいずれかの炭化水素油の流動接触分解触媒。
（ａ）塩基性塩化アルミニウム。
（ｂ）重リン酸アルミニウム。
（ｃ）アルミナゾル。
［８］前記触媒組成物Ａ及び前記触媒組成物Ｂに含まれるゼオライトは、ＦＡＵ型（フォージャサイト型）、ＭＦＩ型、ＣＨＡ型、及びＭＯＲ型のいずれか１又は２以上であり、しかも、前記触媒組成物Ａ及び前記触媒組成物Ｂには、触媒組成基準で、前記ゼオライトが１５〜６０質量％の範囲でそれぞれ含まれていることを特徴とする［１］〜［７］のいずれかの炭化水素油の流動接触分解触媒。
［９］前記ＦＡＵ型のゼオライトは、水素型Ｙ型ゼオライト（ＨＹ）、超安定化Ｙ型ゼオライト（ＵＳＹ）、レアアース交換Ｙ型ゼオライト（ＲＥＹ）、レアアース交換超安定化Ｙ型ゼオライト（ＲＥＵＳＹ）のいずれかであることを特徴とする［８］の炭化水素油の流動接触分解触媒。
［１０］触媒組成物Ａ及び前記触媒組成物Ｂは、前記ゼオライト及び前記結合剤以外に、粘土鉱物を含むことを特徴とする［１］〜［９］のいずれかの炭化水素油の流動接触分解触媒。
［１１］［１］〜［１０］のいずれかの炭化水素油の流動接触分解触媒を使用することを特徴とする炭化水素油の流動接触分解方法。
［１２］前記炭化水素油が残渣油を含むことを特徴とする［１１］の炭化水素油の流動接触分解方法。
［１３］前記炭化水素油には、バナジウム及びニッケルがそれぞれ０．５ｐｐｍ以上含まれていることを特徴とする［１２］の炭化水素油の流動接触分解方法。
［１４］前記流動接触分解触媒には、バナジウム及びニッケルがそれぞれ３００ｐｐｍ以上含まれていることを特徴とする［１１］〜［１３］のいずれかに記載の炭化水素油の流動接触分解方法。K A : K B = 1: 0.5 to 1: 1.5 (3)
[4] The K value (K m ) of the fluid catalytic cracking catalyst is higher than the K value (K A ) of the catalyst composition A and the K value (K B ) of the catalyst composition B. The fluid catalytic cracking catalyst of the hydrocarbon oil according to any one of [1] to [3].
[5] Gasoline yield G m of fluid catalytic cracking catalyst, and wherein the higher than the gasoline yield G B gasoline yield G A and the catalyst composition B of the catalyst composition A [1] ~ [4 ] The fluid catalytic cracking catalyst of any hydrocarbon oil.
[6] The fluid catalytic cracking of the hydrocarbon oil according to any one of [1] to [5], wherein the silica-based binder is one or more of silica sol, water glass, and silicic acid liquid. catalyst.
[7] The fluid contact of the hydrocarbon oil according to any one of [1] to [6], wherein the aluminum compound binder is at least one selected from the group consisting of the following (a) to (c): Cracking catalyst.
(A) Basic aluminum chloride.
(B) Aluminum biphosphate.
(C) Alumina sol.
[8] The zeolite contained in the catalyst composition A and the catalyst composition B is one or more of FAU type (faujasite type), MFI type, CHA type, and MOR type, and Any one of [1] to [7], wherein the catalyst composition A and the catalyst composition B each contain the zeolite in a range of 15 to 60% by mass on the basis of the catalyst composition. Fluid catalytic cracking catalyst of hydrocarbon oil.
[9] The FAU type zeolite includes hydrogen type Y zeolite (HY), ultra-stabilized Y type zeolite (USY), rare earth exchanged Y type zeolite (REY), and rare earth exchanged super stabilized Y type zeolite (REUSY). [8] The fluid catalytic cracking catalyst for hydrocarbon oils according to [8].
[10] The fluid contact of the hydrocarbon oil according to any one of [1] to [9], wherein the catalyst composition A and the catalyst composition B contain a clay mineral in addition to the zeolite and the binder. Cracking catalyst.
[11] A fluid catalytic cracking method for hydrocarbon oil, comprising using the fluid catalytic cracking catalyst for hydrocarbon oil according to any one of [1] to [10].
[12] The fluid catalytic cracking method of hydrocarbon oil according to [11], wherein the hydrocarbon oil includes a residual oil.
[13] The fluid catalytic cracking method of hydrocarbon oil according to [12], wherein the hydrocarbon oil contains 0.5 ppm or more of vanadium and nickel.
[14] The fluid catalytic cracking method for hydrocarbon oils according to any one of [11] to [13], wherein the fluid catalytic cracking catalyst contains 300 ppm or more of vanadium and nickel.
本発明の炭化水素油の流動接触分解触媒においては、分解できる油が異なる２種の触媒組成物、すなわち、シリカ系バインダーを含む触媒組成物Ａと、アルミニウム化合物バインダーを含む触媒組成物Ｂとが混合されているので、炭化水素油を流動接触分解する際には、一方の触媒組成物が分解した油を他方の触媒組成物が分解可能となるため、分解される油がより軽質化されて、ガソリン及び軽油留分が高収率で得られ、また、コークが低収率となり、更には、ボトムの分解能を高く、すなわち、重質留分の生成を抑えることができる。 In the fluid catalytic cracking catalyst for hydrocarbon oils of the present invention, two kinds of catalyst compositions having different oils that can be decomposed, that is, a catalyst composition A containing a silica-based binder and a catalyst composition B containing an aluminum compound binder, As a result, when hydrocracking hydrocarbon oil by fluid catalytic cracking, the oil decomposed by one catalyst composition can be decomposed by the other catalyst composition. In addition, gasoline and light oil fractions can be obtained in high yield, coke can be obtained in low yield, and bottom resolution can be increased, that is, production of heavy fractions can be suppressed.
特に、原料油がバナジウムやニッケル等の被毒金属を多く含む重質油である場合には、アルミナ化合物バインダーを含む触媒組成物Ｂに含まれるアルミナが該被毒金属と結合して無毒化することにより、シリカ系バインダーを含む触媒組成物Ａが前記被毒金属により被毒され難くなり、高ガソリン収率及び低コーク収率を保持したまま、高ガソリン収率及び高軽油留分収率並びに高ボトム分解になると解される。 In particular, when the raw material oil is a heavy oil containing a large amount of poisoning metals such as vanadium and nickel, the alumina contained in the catalyst composition B containing the alumina compound binder is combined with the poisoning metals and detoxified. As a result, the catalyst composition A containing the silica-based binder is not easily poisoned by the poisoning metal, and the high gasoline yield and the high light oil fraction yield and the high gasoline yield and the low coke yield are maintained. It is understood that it becomes high bottom decomposition.
本発明の一実施の形態に係る炭化水素油の流動接触分解触媒は、ゼオライト及び結合剤として１０〜３０質量％のシリカ系バインダーを含む触媒組成物Ａと、ゼオライト及び結合剤として１０〜３０質量％のアルミニウム化合物バインダーを含む触媒組成物Ｂとを、触媒組成物Ａの質量をＷAとし、触媒組成物Ｂの質量をＷBとして、質量比（ＷA：ＷB）が１０：９０〜９０：１０の範囲内で混合したものである。以下、それぞれの触媒組成物について詳しく説明する。The hydrocarbon oil fluid catalytic cracking catalyst according to one embodiment of the present invention includes a catalyst composition A containing 10-30% by mass of a silica-based binder as a zeolite and a binder, and 10-30 masses as a zeolite and a binder. % Of the aluminum compound binder, the mass of the catalyst composition A is W A , the mass of the catalyst composition B is W B , and the mass ratio (W A : W B ) is 10:90 to It is a mixture within the range of 90:10. Hereinafter, each catalyst composition will be described in detail.
なお、流動接触分解装置（実装置）においては、シリカ系バインダーを含む触媒からアルミニウム化合物バインダーを含む触媒又はその逆へと触媒を切り替える際には、他方の触媒が徐々に追加されるため前記した質量比になる場合があるが、本発明においては、所定の質量比で混合された触媒を常時追加する点で異なり、装置内の触媒組成物の質量比は一定に保たれる。 In the fluid catalytic cracking device (actual device), when the catalyst is switched from the catalyst containing the silica-based binder to the catalyst containing the aluminum compound binder or vice versa, the other catalyst is gradually added. The mass ratio may be different, but the present invention is different in that a catalyst mixed at a predetermined mass ratio is always added, and the mass ratio of the catalyst composition in the apparatus is kept constant.
また、本発明の触媒はバインダーが異なる触媒組成物を混合したものであって、それらは流動接触分解をおこなうものであり、流動接触分解触媒の性能を補うために添加されるアディティブ触媒（添加触媒）とは異なる。
［触媒組成物Ａについて］
触媒組成物Ａは、例えば、ゼオライトを１５〜６０質量％、好ましくは２０〜５０質量％、結合剤としてシリカ系バインダーを１０〜３０質量％、好ましくは１５〜２５質量％、残りはゼオライトを除く無機酸化物を含んでいる。
《シリカ系バインダー》
シリカ系バインダーとしては、シリカゾル、水ガラス（ケイ酸ナトリウム）、及び、ケイ酸液のいずれか１又は２以上を使用することができる。また、シリカゾルは水ガラスから作製することができる。また、例えば、ＳｉＯ2濃度が１０〜１５質量％のシリカゾルは、ＳｉＯ2濃度が１２〜２３質量％の水ガラスと、濃度２０〜３０質量％の硫酸とを同時に連続的に加えて調製することができる。
《ゼオライト》
ここで、ゼオライトとしては、通常、炭化水素油の接触分解触媒に使用されるゼオライトを用いることが可能で、例えば、ＦＡＵ型（フォージャサイト型。例えば、Ｙ型ゼオライト、Ｘ型ゼオライト等）、ＭＦＩ型（例えば、ＺＳＭ−５、ＴＳ−１等）、ＣＨＡ型(。例えば、チャバサイト、ＳＡＰＯ−３４等)、及びＭＯＲ型（例えば、モルデナイト、Ｃａ−Ｑ等）のいずれか１又は２以上であり、特にＦＡＵ型が好ましい。フォージャサイト型のゼオライトは、水素型Ｙ型ゼオライト（ＨＹ）、超安定化Ｙ型ゼオライト（ＵＳＹ）や、ＨＹ及びＵＳＹにそれぞれ希土類金属をイオン交換等により担持させたレアアース交換Ｙ型ゼオライト（ＲＥＹ）、レアアース交換超安定化Ｙ型ゼオライト（ＲＥＵＳＹ）がある。Further, the catalyst of the present invention is a mixture of catalyst compositions having different binders, which are subjected to fluid catalytic cracking, and an additive catalyst (added catalyst added to supplement the performance of fluid catalytic cracking catalyst) ) Is different.
[Catalyst composition A]
The catalyst composition A is, for example, 15 to 60% by mass of zeolite, preferably 20 to 50% by mass, 10 to 30% by mass of silica-based binder as a binder, preferably 15 to 25% by mass, and the rest excludes zeolite. Contains inorganic oxides.
<Silica-based binder>
As the silica-based binder, one or more of silica sol, water glass (sodium silicate), and silicate liquid can be used. Silica sol can be prepared from water glass. For example, a silica sol having a SiO 2 concentration of 10 to 15% by mass is prepared by continuously adding water glass having a SiO 2 concentration of 12 to 23% by mass and sulfuric acid having a concentration of 20 to 30% by mass simultaneously. Can do.
<< Zeolite >>
Here, as the zeolite, it is possible to use a zeolite that is usually used as a catalytic cracking catalyst for hydrocarbon oils. For example, FAU type (faujasite type. For example, Y type zeolite, X type zeolite, etc.) One or more of MFI type (for example, ZSM-5, TS-1 etc.), CHA type (for example, chabasite, SAPO-34 etc.), and MOR type (for example, mordenite, Ca-Q etc.) In particular, the FAU type is preferable. The faujasite-type zeolite includes hydrogen-type Y zeolite (HY), ultra-stabilized Y-type zeolite (USY), and rare earth-exchanged Y-type zeolite (REY) in which rare earth metals are supported on HY and USY by ion exchange, respectively. ), Rare earth exchange ultra-stabilized Y-type zeolite (REUSY).
触媒組成物Ａに対するゼオライトの含有量が、１５質量％未満では分解活性が低くなる傾向にあり、また、６０質量％を超えると嵩密度が高くなると共に強度が低くなる傾向にある。
《無機酸化物》
無機酸化物としては、カオリンなどの粘土鉱物の他に、活性アルミナ、多孔性シリカ、希土類金属化合物、及び金属補足剤（メタルトラップ剤）を使用することができる。When the content of the zeolite with respect to the catalyst composition A is less than 15% by mass, the decomposition activity tends to be low, and when it exceeds 60% by mass, the bulk density tends to be high and the strength tends to be low.
<Inorganic oxide>
As inorganic oxides, activated alumina, porous silica, rare earth metal compounds, and metal scavengers (metal trapping agents) can be used in addition to clay minerals such as kaolin.
希土類金属酸化物は、触媒組成物Ａに、ＲＥ2Ｏ3として０．５〜２．０質量％となるように含まれてもよい。ここで、希土類金属としては、セリウム（Ｃｅ）、ランタン（Ｌａ）、プラセオジウム（Ｐｒ）、及びネオジム（Ｎｄ）等が挙げられ、これらは単独ないし２種以上の金属酸化物として担持することができる。The rare earth metal oxide may be contained in the catalyst composition A so as to be 0.5 to 2.0 mass% as RE 2 O 3 . Here, examples of the rare earth metal include cerium (Ce), lanthanum (La), praseodymium (Pr), neodymium (Nd), and the like, and these can be supported alone or as two or more metal oxides. .
触媒組成物Ａの製造方法の一例を以下に示す。まず、前記したシリカゾル（シリカ系バインダーの一例）に、カオリン、多孔性シリカ粉、及び活性アルミナを加え、更に２０〜３０質量％硫酸でｐＨ３〜５に調製した超安定化Ｙ型ゼオライト（ＵＳＹ）スラリーを加えて、混合スラリーを調製する。この混合スラリーを噴霧乾燥して球状粒子を得る。得られた球状粒子を洗浄し、更に希土類金属（Rare Earth。ＲＥ）塩化物の水溶液と接触させて、ＲＥ2Ｏ3として０．５〜２．０質量％となるようにイオン交換した後、乾燥して、触媒組成物Ａを得る。得られた触媒組成物Ａの平均粒子径は、後述する触媒組成物Ｂと混合できる範囲であれば特に制限されないが、６０〜７０μｍ程度である。
［触媒組成物Ｂについて］
触媒組成物Ｂは、例えば、ゼオライトを１５〜６０質量％、好ましくは２０〜５０質量％、結合剤としてアルミニウム化合物バインダーを１０〜３０質量％、好ましくは１５〜２５質量％、残りはゼオライトを除く無機酸化物を含んでいる。
《アルミニウム化合物バインダー》
アルミニウム化合物バインダーとしては、（ａ）塩基性塩化アルミニウム、（ｂ）重リン酸アルミニウム、（ｃ）アルミナゾルがある。また、アルミニウム化合物バインダーとして、ジブサイト、バイアライト、ベーマイト等の結晶性アルミナのいずれか１又は２以上を酸溶液中に溶解させた溶液を使用することもできる。An example of the manufacturing method of the catalyst composition A is shown below. First, ultra-stabilized Y-type zeolite (USY) prepared by adding kaolin, porous silica powder, and activated alumina to the above silica sol (an example of a silica-based binder) and further adjusting the pH to 3 to 5 with 20 to 30% by mass sulfuric acid. Add the slurry to prepare a mixed slurry. The mixed slurry is spray-dried to obtain spherical particles. The obtained spherical particles were washed, further contacted with an aqueous solution of rare earth metal (Rare Earth.RE) chloride, and ion-exchanged to give 0.5 to 2.0 mass% as RE 2 O 3 , Dry to obtain catalyst composition A. Although the average particle diameter of the obtained catalyst composition A will not be restrict | limited especially if it is a range which can be mixed with the catalyst composition B mentioned later, it is about 60-70 micrometers.
[Catalyst composition B]
In the catalyst composition B, for example, zeolite is 15 to 60% by mass, preferably 20 to 50% by mass, an aluminum compound binder as a binder is 10 to 30% by mass, preferably 15 to 25% by mass, and the rest excludes zeolite. Contains inorganic oxides.
《Aluminum compound binder》
Examples of the aluminum compound binder include (a) basic aluminum chloride, (b) aluminum biphosphate, and (c) alumina sol. Moreover, as an aluminum compound binder, the solution which melt | dissolved any 1 or 2 or more of crystalline aluminas, such as a dibsite, a bayerite, and a boehmite, in an acid solution can also be used.
ここで、塩基性塩化アルミニウムは式４で示される。 Here, basic aluminum chloride is represented by Formula 4.
［Ａｌ2（ＯＨ）nＣｌ6-n］m・・・（４）
（ただし、０＜ｎ＜６、１≦ｍ≦１０、好ましくは４．８≦ｎ≦５．３、３≦ｍ≦７である。なお、ｍは、自然数を示す。）
重リン酸アルミニウムは、リン酸二水素アルミニウム、第一リン酸アルミニウムともいわれ、Ａｌ（Ｈ2ＰＯ4）3で示される。アルミナゾルは、例えば、擬ベーマイト型アルミナを酸でｐＨ調整して作製することができる。
《ゼオライト及び無機酸化物》
触媒組成物Ｂに使用されるゼオライト及び無機酸化物については、前記した触媒組成物Ａと同様のものが使用でき、それらの含有量についても触媒組成物Ａと同様に調製することができる。[Al 2 (OH) n Cl 6-n ] m (4)
(However, 0 <n <6, 1 ≦ m ≦ 10, preferably 4.8 ≦ n ≦ 5.3, 3 ≦ m ≦ 7, where m represents a natural number.)
The heavy aluminum phosphate is also called aluminum dihydrogen phosphate or primary aluminum phosphate, and is represented by Al (H 2 PO 4 ) 3 . The alumina sol can be produced, for example, by adjusting the pH of pseudo boehmite type alumina with an acid.
<< Zeolite and inorganic oxide >>
About the zeolite and inorganic oxide which are used for the catalyst composition B, the thing similar to the above-mentioned catalyst composition A can be used, About those content, it can prepare similarly to the catalyst composition A.
触媒組成物Ｂの製造方法の一例を以下に示す。まず、例えば、Ａｌ2Ｏ3濃度が２０〜２５質量％の塩基性塩化アルミニウム溶液（アルミニウム化合物バインダーの一例）に、カオリン、活性アルミナ、ＵＳＹスラリーを加えて、スラリー濃度が３５〜４５％である混合スラリーを調製する。この混合スラリーを噴霧乾燥して球状粒子を得る。この球状粒子を洗浄し、更に希土類金属塩化物水溶液と接触させてＲＥ2Ｏ3として０．５〜２．０質量％となるようにイオン交換した後、乾燥して触媒組成物Ｂを得る。得られた触媒組成物Ｂの平均粒子径は、特に制限されないが、６０〜７０μｍ程度である。
［流動接触分解触媒］
本発明の流動接触分解触媒は、触媒組成物Ａと触媒組成物Ｂとを、触媒組成物Ａの質量をＷAとし、触媒組成物Ｂの質量をＷBとして、質量比（ＷA：ＷB）が１０：９０〜９０：１０の範囲内で混合したものであって、各触媒組成物の質量割合が所定範囲外の場合には、各触媒組成物を単独で流動接触分解に用いた場合との差異が小さくなり、明確な効果が得られ難くなる。なお、触媒組成物Ａと触媒組成物Ｂとの混合割合（質量比）は、炭化水素油を本流動接触分解触媒により分解して得られる分解生成物（特に、ガソリン、ＬＣＯ）が所望の組成（収率）となるように決めるのがよい。
［流動接触分解方法］
本発明の流動接触分解触媒を使用した流動接触分解においては、通常の炭化水素油の流動接触分解条件を採用することができ、例えば、以下に述べる条件が好適に採用できる。An example of the manufacturing method of the catalyst composition B is shown below. First, for example, kaolin, activated alumina, and USY slurry are added to a basic aluminum chloride solution (an example of an aluminum compound binder) having an Al 2 O 3 concentration of 20 to 25% by mass, and the slurry concentration is 35 to 45%. A mixed slurry is prepared. The mixed slurry is spray-dried to obtain spherical particles. The spherical particles are washed, further contacted with a rare earth metal chloride aqueous solution to perform ion exchange so that the RE 2 O 3 is 0.5 to 2.0% by mass, and then dried to obtain a catalyst composition B. The average particle size of the obtained catalyst composition B is not particularly limited, but is about 60 to 70 μm.
[Fluid catalytic cracking catalyst]
Fluid catalytic cracking catalyst of the present invention, a catalyst composition A and the catalyst composition B, the weight of the catalyst composition A and W A, the weight of the catalyst composition B as W B, the mass ratio (W A: W B ) was mixed within the range of 10:90 to 90:10, and when the mass ratio of each catalyst composition was outside the predetermined range, each catalyst composition was used alone for fluid catalytic cracking. The difference from the case becomes small, and it becomes difficult to obtain a clear effect. The mixing ratio (mass ratio) of the catalyst composition A and the catalyst composition B is such that the cracked product (particularly gasoline, LCO) obtained by cracking hydrocarbon oil with the present fluid catalytic cracking catalyst has a desired composition. (Yield) should be determined.
[Fluid catalytic cracking method]
In fluid catalytic cracking using the fluid catalytic cracking catalyst of the present invention, the usual fluid catalytic cracking conditions of hydrocarbon oil can be employed, and for example, the conditions described below can be suitably employed.
接触分解に使用される原料油としては、通常の炭化水素原料油、例えば、水素化脱硫減圧蒸留軽油（ＤＳＶＧＯ）や、減圧蒸留軽油（ＶＧＯ）を用いることができ、更に、常圧蒸留残渣油（ＡＲ）、減圧蒸留残渣油（ＶＲ）、脱硫常圧蒸留残渣油（ＤＳＡＲ）、脱硫減圧蒸留残渣油（ＤＳＶＲ）、脱アスファルテン油（ＤＡＯ）等の残渣油も使用することができ、これらの単独又は混合したものも使用できる。なお、本発明の流動接触分解触媒においては、ニッケル及びバナジウムがそれぞれ０．５ｐｐｍ以上含まれている残渣油も処理可能であり、原料油として残渣油を単独で用いる残渣油接触分解装置（Ｒｅｓｉｄ ＦＣＣ。ＲＦＣＣ）にも使用できる。ここで、従来の流動接触分解触媒をＲＦＣＣで使用した場合には、残渣油中のニッケル及びバナジウムが触媒に付着して活性が低下するが、本発明の流動接触分解触媒では、バナジウム及びニッケルがそれぞれ０．５ｐｐｍ以上含有している残渣油を処理しても、優れた触媒性能を保持できる。また、本発明の流動接触分解触媒は、バナジウム及びニッケルがそれぞれ３００ｐｐｍ以上含有されていても触媒性能を保持できる。本発明の流動接触分解触媒に含有されるバナジウム及びニッケルの上限は、それぞれ１００００ｐｐｍ程度である。 As the feedstock used for the catalytic cracking, a normal hydrocarbon feedstock such as hydrodesulfurization vacuum distillation gas oil (DSVGO) or vacuum distillation gas oil (VGO) can be used, and further, atmospheric distillation residue oil. (AR), vacuum distillation residue oil (VR), desulfurization atmospheric distillation residue oil (DSAR), desulfurization vacuum distillation residue oil (DSVR), deasphaltenic oil (DAO), and other residual oils can be used. A single material or a mixture thereof can be used. In the fluid catalytic cracking catalyst of the present invention, a residual oil containing 0.5 ppm or more of nickel and vanadium can be treated, and a residual oil catalytic cracking apparatus (Resid FCC) that uses the residual oil alone as a raw material oil. RFCC). Here, when a conventional fluid catalytic cracking catalyst is used in RFCC, nickel and vanadium in the residual oil adhere to the catalyst and the activity is reduced. However, in the fluid catalytic cracking catalyst of the present invention, vanadium and nickel are Even if the residual oils containing 0.5 ppm or more are treated, excellent catalyst performance can be maintained. Further, the fluid catalytic cracking catalyst of the present invention can maintain the catalytic performance even when vanadium and nickel are contained in an amount of 300 ppm or more. The upper limits of vanadium and nickel contained in the fluid catalytic cracking catalyst of the present invention are each about 10000 ppm.
また、前述の炭化水素原料油を接触分解する際の反応温度は４７０〜５５０℃の範囲が好適に採用され、反応圧力は一般的にはおよそ１〜３ｋｇ／ｃｍ2の範囲が好適であり、触媒／油の質量比（触媒／油比）は２．５〜７．０の範囲が好ましく、更に接触時間は１０〜６０ｈｒ-1の範囲が好ましい。
《Ｋ値》
Ｋ値は、前記した方法で原料油を接触分解して、ガソリンの沸点（３０〜２２０℃程度）以上の留分である灯軽油留分（ＬＣＯ）と重質油留分（ＨＣＯ）の質量を測定し、原料油の質量とから式（２）により転化率を求め、転化率から式（１）により求めることができる。Further, the reaction temperature when catalytically cracking the above hydrocarbon feedstock is preferably employed in the range of 470 to 550 ° C., and the reaction pressure is generally preferably in the range of about 1 to 3 kg / cm 2 . The catalyst / oil mass ratio (catalyst / oil ratio) is preferably in the range of 2.5 to 7.0, and the contact time is preferably in the range of 10 to 60 hr −1 .
<< K value >>
K value is the mass of kerosene oil fraction (LCO) and heavy oil fraction (HCO), which are fractions higher than the boiling point of gasoline (about 30-220 ° C) by catalytic cracking of the raw oil by the method described above. And the conversion rate can be obtained from the mass of the raw material oil by the equation (2) and can be obtained from the conversion rate by the equation (1).
Ｋ＝転化率／（１００−転化率）・・・（１）
転化率（質量％）＝（ａ−ｂ）／ａ×１００・・・（２）
但し、ａは原料油の質量、ｂは灯軽油留分及び重質留分の合計の質量である。K = conversion / (100-conversion) (1)
Conversion (mass%) = (ab) / a × 100 (2)
However, a is the mass of raw material oil, b is the total mass of a kerosene oil fraction and a heavy fraction.
ここで、触媒組成物Ａ及び触媒組成物ＢのＫ値（それぞれＫA、ＫB）は、１以上（すなわち、転化率５０％以上）、好ましくは１．５以上（すなわち、転化率６０％以上）、より好ましくは２．３以上（すなわち、転化率７０％以上）がよい。触媒組成物Ａ及び触媒組成物ＢのＫ値が、１未満（すなわち、転化率５０％未満）の場合には、ガソリンやＬＣＯの収率が低いため実用的でない。Here, the K values (K A and K B ) of the catalyst composition A and the catalyst composition B are 1 or more (that is,
また、触媒組成物Ａ及び触媒組成物ＢのＫ値はＫA：ＫBが１：０．５〜１：１．５、好ましくは１：０．８〜１：１．２、より好ましくは１：０．９〜１：１．１がよい。ここで、ＫA：ＫB＜１：０．５の場合及びＫA：ＫB＞１：１．５の場合には、両触媒組成物のＫ値の差が大きすぎるため、ＫA及びＫBを超えることが難しくなる。Further, the catalyst composition K values of A and catalyst composition B K A: K B is 1: 0.5 to 1: 1.5, preferably 1: 0.8 to 1: 1.2, more preferably 1: 0.9 to 1: 1.1 is preferable. Here, K A: K B <1 : 0.5 in the case and K A: K B> 1: In the case of 1.5, since the difference in K values of both the catalyst composition is too high, K A and it is difficult to exceed K B.
更に、流動接触分解触媒のＫ値（Ｋm）が、触媒組成物ＡのＫ値（ＫA）及び触媒組成物ＢのＫ値（ＫB）よりも高いのが好ましい。
《ガソリン収率Ｇ》
流動接触分解触媒のガソリン収率Ｇmが、触媒組成物Ａのガソリン収率ＧA及び触媒組成物Ｂのガソリン収率ＧBよりも高いのが好ましい。ここで、ガソリン収率は、前記した方法で原料油を接触分解し、得られたガソリンの質量と、原料油の質量とから計算される。Further, the K value (K m ) of the fluid catalytic cracking catalyst is preferably higher than the K value (K A ) of the catalyst composition A and the K value (K B ) of the catalyst composition B.
<< Gasoline yield G >>
Gasoline yield G m of fluid catalytic cracking catalyst is higher is preferred than the gasoline yield G B gasoline yield G A and the catalyst composition B of the catalyst composition A. Here, the gasoline yield is calculated from the mass of gasoline obtained by catalytically cracking the feedstock by the above-described method and the mass of the feedstock.
また、本発明の流動接触分解触媒は、触媒組成物Ａ及び触媒組成物Ｂの単独のものよりもＬＣＯ収率が高くなる傾向にあり、逆に、水素収率、Ｃ１＋Ｃ２収率、ＬＰＧ収率、ＨＣＯ収率、及びコーク収率が低くなる傾向にある。すなわち、本発明の流動接触分解触媒は、触媒組成物Ａ及び触媒組成物Ｂの単独よりも、ガソリンやＬＣＯなどの液体燃料の収率が増える傾向にあるが、ガスや重質油、コークなどの収率は低くなる傾向にある。 Further, the fluid catalytic cracking catalyst of the present invention tends to have a higher LCO yield than that of the catalyst composition A and the catalyst composition B alone, and conversely, the hydrogen yield, the C1 + C2 yield, the LPG yield. , HCO yield, and coke yield tend to be low. That is, the fluid catalytic cracking catalyst of the present invention tends to increase the yield of liquid fuel such as gasoline and LCO as compared with the catalyst composition A and the catalyst composition B alone, but gas, heavy oil, coke, etc. Yield tends to be low.
［シリカ系バインダーの作製］
《触媒組成物Ａ1》
ＳｉＯ2濃度が１７質量％の水ガラス２９４１ｇと、濃度２５質量％の硫酸１０５９ｇとを同時に連続的に加えて、ＳｉＯ2濃度が１２．５質量％のシリカゾル（シリカ系バインダーの一例）４０００ｇを調製した。このシリカゾルに乾燥基準でカオリン８００ｇ、多孔性シリカ粉１７５ｇ、及び活性アルミナ２５０ｇを加え、更に２５質量％の硫酸でｐＨ３．９に調製した超安定化Ｙ型ゼオライト（ＵＳＹ）スラリー８００ｇを加えて混合スラリーを調製した。この混合スラリーを噴霧乾燥して平均粒子径６０μｍの球状粒子を得た。[Preparation of silica binder]
"Catalyst composition A 1"
2941 g of water glass having a SiO 2 concentration of 17% by mass and 1059 g of sulfuric acid having a concentration of 25% by mass are continuously added simultaneously to prepare 4000 g of silica sol (an example of a silica-based binder) having a SiO 2 concentration of 12.5% by mass. did. 800 g of kaolin, 175 g of porous silica powder, and 250 g of activated alumina are added to this silica sol on a dry basis, and 800 g of ultra-stabilized Y-type zeolite (USY) slurry adjusted to pH 3.9 with 25% by mass sulfuric acid is added and mixed. A slurry was prepared. This mixed slurry was spray-dried to obtain spherical particles having an average particle size of 60 μm.
得られた球状粒子を洗浄し、更に希土類金属（Rare Earth。ＲＥ）塩化物の水溶液（セリウム及びランタンの塩化物を含む。以下同様）と接触させて、ＲＥ2Ｏ3として１．０質量％となるようにイオン交換した後、１３５℃の乾燥機で乾燥して、触媒組成物Ａ1を調製した。The obtained spherical particles were washed, and further contacted with an aqueous solution of rare earth metal (Rare Earth.RE) chloride (including cerium and lanthanum chlorides, the same applies hereinafter) to give 1.0% by mass as RE 2 O 3. After ion exchange so as to be, the catalyst composition A 1 was prepared by drying with a dryer at 135 ° C.
触媒組成物Ａ1の組成は、シリカゾル由来のＳｉＯ2が２０質量％、カオリンが３２質量％、多孔性シリカ粉由来のＳｉＯ2が７質量％、活性アルミナが１０質量％、ＵＳＹが３０質量％であった。ここで、表１に触媒組成物Ａ1の性状を示す。
《触媒組成物Ａ2》
ＳｉＯ2濃度が１７質量％の水ガラス２９４１ｇと、濃度２５質量％の硫酸１０５９ｇとを同時に連続的に加えて、ＳｉＯ2濃度が１２．５質量％のシリカゾル（シリカ系バインダーの一例）４０００ｇを調製した。このシリカゾルに乾燥基準でカオリン８００ｇ、多孔性シリカ粉１７５ｇ、及び活性アルミナ２５０ｇを加え、更に２５質量％硫酸でｐＨ３．９に調製した超安定化ＲＥＹ型ゼオライト（ＲＥＵＳＹ）スラリーをＹ型ゼオライトとして８００ｇを加えて混合スラリーを調製した。この混合スラリーを噴霧乾燥して平均粒子径６０μｍの球状粒子を得た。The composition of the catalyst composition A 1 is 20% by mass of SiO 2 derived from silica sol, 32% by mass of kaolin, 7% by mass of SiO 2 derived from porous silica powder, 10% by mass of activated alumina, and 30% by mass of USY. Met. Here, Table 1 shows properties of the catalyst composition A 1 .
"Catalyst composition A 2"
2941 g of water glass having a SiO 2 concentration of 17% by mass and 1059 g of sulfuric acid having a concentration of 25% by mass are continuously added simultaneously to prepare 4000 g of silica sol (an example of a silica-based binder) having a SiO 2 concentration of 12.5% by mass. did. To this silica sol, 800 g of kaolin, 175 g of porous silica powder, and 250 g of activated alumina were added on a dry basis, and 800 g of ultra-stabilized REY zeolite (REUSY) slurry prepared to pH 3.9 with 25% by mass sulfuric acid as Y zeolite. Was added to prepare a mixed slurry. This mixed slurry was spray-dried to obtain spherical particles having an average particle size of 60 μm.
得られた球状粒子を洗浄した後、１３５℃の乾燥機で乾燥して、触媒組成物Ａ2を調製した。ここで、表１に触媒組成物Ａ2の性状を示す。
《触媒組成物Ａ3》
ＳｉＯ2濃度が１７質量％の水ガラス（シリカ系バインダーの一例）２９４１ｇに乾燥基準でカオリン８００ｇ、多孔性シリカ粉１７５ｇ、及び活性アルミナ２５０ｇを加え、更に２５質量％硫酸でｐＨ３．９に調製した超安定化ＲＥＹ型ゼオライト（ＲＥＵＳＹ）スラリーをＹ型ゼオライトとして８００ｇを加えて混合スラリーを調製した。この混合スラリーを噴霧乾燥して平均粒子径６０μｍの球状粒子を得た。The obtained spherical particles were washed and then dried with a dryer at 135 ° C. to prepare catalyst composition A 2 . Here, the properties of the catalyst composition A 2 in Table 1.
"Catalyst composition A 3"
800 g of kaolin, 175 g of porous silica powder, and 250 g of activated alumina were added to 2941 g of water glass (an example of a silica-based binder) having a SiO 2 concentration of 17% by mass, and further adjusted to pH 3.9 with 25% by mass sulfuric acid. 800 g of ultra-stabilized REY-type zeolite (REUSY) slurry was added as a Y-type zeolite to prepare a mixed slurry. This mixed slurry was spray-dried to obtain spherical particles having an average particle size of 60 μm.
得られた球状粒子を洗浄した後、１３５℃の乾燥機で乾燥して、触媒組成物Ａ3を調製した。ここで、表１に触媒組成物Ａ3の組成の性状を示す。The obtained spherical particles were washed and then dried with a dryer at 135 ° C. to prepare catalyst composition A 3 . Here, the properties of the composition of the catalyst composition A 3 in Table 1.
但し、比表面積はＢＥＴ法で、嵩比重はＵＯＰ法２５４−６５でそれぞれ測定した。また、焼成減量は、１０００℃で１時間焼成した際の減量された質量を示す。（以下同様）
［アルミニウム化合物バインダーの作製］
《触媒組成物Ｂ1》
Ａｌ2Ｏ3濃度が２３．３質量％の塩基性塩化アルミニウム溶液（アルミニウム化合物バインダーの一例）１２０１ｇに、カオリン８４０ｇ、活性アルミナ２６０ｇ、ＵＳＹスラリー６４０ｇを加えて、スラリー濃度が４１％である混合スラリーを調製した。この混合スラリーを噴霧乾燥して平均粒子径６０μｍの球状粒子を得た。この球状粒子を洗浄し、更に希土類金属塩化物水溶液と接触させてＲＥ2Ｏ3として１．０質量％となるようにイオン交換した後、乾燥機により１３５℃で乾燥して触媒組成物Ｂ１を調製した。得られた触媒組成物Ｂ1の組成は、塩基性塩化アルミニウム溶液由来のＡｌ2Ｏ3が１４質量％、カオリンが４１質量％、活性アルミナが１３質量％、ＵＳＹが３２質量％であった。また、表２に触媒組成物Ｂ1の性状を示す。
《触媒組成物Ｂ2》
Ａｌ2Ｏ3濃度が２３．３質量％の塩基性塩化アルミニウム溶液（アルミニウム化合物バインダーの一例）１２０１ｇに、カオリン８４０ｇ、活性アルミナ２６０ｇ、ＲＥＵＳＹスラリーをＹ型ゼオライトとして６４０ｇを加えて、スラリー濃度が４３％である混合スラリーを調製した。この混合スラリーを噴霧乾燥して平均粒子径６０μｍの球状粒子を得た。この球状粒子を洗浄した後、乾燥機により１３５℃で乾燥して触媒組成物Ｂ2を調製した。ここで、表２に触媒組成物Ｂ2の性状を示す。
《触媒組成物Ｂ3》
Ａｌ2Ｏ3濃度が１２．５質量％の擬ベーマイト型アルミナ（Ｓａｓｏｌ社製Ｃａｔａｐａｌ−Ａ）水溶液２４００ｇに６３％硝酸でｐＨ３．０にしてアルミナゾル（アルミニウム化合物バインダーの一例）を調製した。このアルミナゾルに、カオリン８４０ｇ、活性アルミナ２６０ｇ、ＲＥＵＳＹスラリーをＹ型ゼオライトとして６４０ｇを加えて、スラリー濃度が４３％である混合スラリーを調製した。この混合スラリーを噴霧乾燥して平均粒子径６０μｍの球状粒子を得た。この球状粒子を電気炉により６００℃で焼成して触媒組成物Ｂ3を調製した。ここで、表２に触媒組成物Ｂ3の性状を示す。
《触媒組成物Ｂ4》
１７．４質量％の重リン酸アルミニウム溶液（アルミニウム化合物バインダーの一例）１７２３ｇに、カオリン８４０ｇ、活性アルミナ２６０ｇ、ＲＥＵＳＹスラリーをＹ型ゼオライトとして６４０ｇを加えて、スラリー濃度が４３％である混合スラリーを調製した。この混合スラリーを噴霧乾燥して平均粒子径６０μｍの球状粒子を得た。この球状粒子を電気炉により６００℃で焼成して触媒組成物Ｂ4を調製した。ここで、表２に触媒組成物Ｂ4の性状を示す。However, the specific surface area was measured by the BET method, and the bulk specific gravity was measured by the UOP method 254-65. Further, the weight loss by firing indicates the weight reduced when firing at 1000 ° C. for 1 hour. (The same applies hereinafter)
[Preparation of aluminum compound binder]
"Catalyst composition B 1"
A mixed slurry in which 840 g of kaolin, 260 g of activated alumina, and 640 g of USY slurry are added to 1201 g of a basic aluminum chloride solution (an example of an aluminum compound binder) having an Al 2 O 3 concentration of 23.3 mass%, and the slurry concentration is 41%. Was prepared. This mixed slurry was spray-dried to obtain spherical particles having an average particle size of 60 μm. The spherical particles were washed, further contacted with a rare earth metal chloride aqueous solution to exchange ions so that the RE 2 O 3 was 1.0% by mass, and then dried at 135 ° C. with a dryer to obtain the catalyst composition B1. Prepared. The composition of the obtained catalyst composition B 1 was 14% by mass of Al 2 O 3 derived from the basic aluminum chloride solution, 41% by mass of kaolin, 13% by mass of activated alumina, and 32% by mass of USY. Also shows the properties of the catalyst composition B 1 in Table 2.
"Catalyst composition B 2"
To 1201 g of a basic aluminum chloride solution (an example of an aluminum compound binder) having an Al 2 O 3 concentration of 23.3 mass%, 840 g of kaolin, 260 g of activated alumina, and 640 g of REUSY slurry as Y-type zeolite are added, and the slurry concentration is 43. % Mixed slurry was prepared. This mixed slurry was spray-dried to obtain spherical particles having an average particle size of 60 μm. After washing the spherical particles, to prepare a catalyst composition B 2 and dried at 135 ° C. The dryer. Here, the properties of the catalyst composition B 2 in Table 2.
"Catalyst composition B 3"
An alumina sol (an example of an aluminum compound binder) was prepared by adjusting pH to 3.0 with 63% nitric acid in 2400 g of an aqueous pseudoboehmite type alumina (Catapal-A manufactured by Sasol) having an Al 2 O 3 concentration of 12.5% by mass. To this alumina sol, 840 g of kaolin, 260 g of activated alumina, and 640 g of REUSY slurry as Y-type zeolite were added to prepare a mixed slurry having a slurry concentration of 43%. This mixed slurry was spray-dried to obtain spherical particles having an average particle size of 60 μm. The spherical particles were calcined at 600 ° C. with an electric furnace to prepare catalyst composition B 3 . Here, properties of the catalyst composition B 3 are shown in Table 2.
"Catalyst composition B 4"
To 1723 g of 17.4 mass% aluminum biphosphate solution (an example of an aluminum compound binder), 840 g of kaolin, 260 g of activated alumina, and 640 g of REUSY slurry as a Y-type zeolite are added to obtain a mixed slurry having a slurry concentration of 43%. Prepared. This mixed slurry was spray-dried to obtain spherical particles having an average particle size of 60 μm. The spherical particles were calcined at 600 ° C. in an electric furnace to prepare catalyst composition B 4 . Here, the properties of the catalyst composition B 4 in Table 2.
《実験例１：Ａ1−Ｂ1》
（実施例１：触媒１）
触媒組成物Ａ1と触媒組成物Ｂ1とを、乾燥基準で質量比が７０：３０となるように混合し、流動接触分解触媒１を調製した。
（実施例２：触媒２）
触媒組成物Ａ1と触媒組成物Ｂ1とを、乾燥基準で質量比が５０：５０となるように混合し、流動接触分解触媒２を調製した。
（実施例３：触媒３）
触媒組成物Ａ1と触媒組成物Ｂ1とを、乾燥基準で質量比が３０：７０となるように混合し、流動接触分解触媒３を調製した。
（比較例１：触媒４）
触媒組成物Ａ1を流動接触分解触媒４とした。
（比較例２：触媒５）
触媒組成物Ｂ1を流動接触分解触媒５とした。
（試験例１）
流動接触分解触媒１〜５について、パイロット反応試験装置（ＡＲＣＯ社製）を用い、同一原料油、同一反応条件下でそれぞれ接触分解反応試験を行った。パイロット反応試験装置は触媒が装置内を循環しながら反応と触媒再生を交互に繰り返す循環式流動床であり、商業規模で使用される流動接触分解装置を模したものである。（以下の実施例も同様である）
まず、反応試験前に、流動接触分解触媒１〜５に、質量基準でオクチル酸バナジウムをＶとして４０００質量ｐｐｍ、また、オクチル酸ニッケルをＮｉとして２０００質量ｐｐｍ含有されるようにサイクリックメタルデポジション（cyclic metal deposition。ＣＭＤ）法により前処理を行った。ここで、ＣＭＤ法とは、少量のバナジウム及びニッケルを流動接触分解触媒に含浸することと、高温で流動接触分解触媒を再生することを繰り返して、流動接触分解触媒にバナジウム及びニッケルを目的濃度となるまで堆積させた後、４００〜８００℃の高温で酸化還元を繰り返す方法であり、商業規模で使用される流動接触分解装置を模したものである。（以下の実施例も同様である）
ここで、表３に示す反応条件により流動接触分解を行った。表４、図１、図２にその反応結果を示す。ここで、表４において、触媒１〜３の計算値とは、触媒４（すなわち、触媒組成物Ａ1のみ）と、触媒５（すなわち、触媒組成物Ｂ1のみ）のそれぞれの反応試験結果から各触媒の混合率により算出（加重平均）したものである（以下の実施例についても同様である）。但し、各Ｋ値については、転化率より計算した。<< Experimental Example 1: A 1 -B 1 >>
(Example 1: Catalyst 1)
Catalyst composition A 1 and catalyst composition B 1 were mixed so that the mass ratio was 70:30 on a dry basis to prepare fluid catalytic cracking
(Example 2: Catalyst 2)
Catalyst composition A 1 and catalyst composition B 1 were mixed so that the mass ratio was 50:50 on a dry basis to prepare fluid catalytic cracking catalyst 2.
(Example 3: Catalyst 3)
Catalyst composition A 1 and catalyst composition B 1 were mixed so that the mass ratio was 30:70 on a dry basis to prepare fluid catalytic cracking catalyst 3.
(Comparative Example 1: Catalyst 4)
The catalyst composition A 1 was fluidized catalytic cracking catalyst 4.
(Comparative Example 2: Catalyst 5)
The catalyst composition B 1 was designated as fluid catalytic cracking catalyst 5.
(Test Example 1)
About the fluid catalytic cracking catalysts 1-5, the catalytic cracking reaction test was each performed on the same feedstock and the same reaction conditions using the pilot reaction test apparatus (made by ARCO). The pilot reaction test apparatus is a circulating fluidized bed in which a catalyst circulates in the apparatus and alternately repeats reaction and catalyst regeneration, and imitates a fluid catalytic cracking apparatus used on a commercial scale. (The following examples are also the same)
First, before the reaction test, cyclic metal deposition is performed so that the fluid catalytic cracking
Here, fluid catalytic cracking was performed under the reaction conditions shown in Table 3. The reaction results are shown in Table 4, FIG. 1 and FIG. Here, in Table 4, the calculated values of the
また、表４におけるＫ値について図１に図示し、ガソリン収率について図２に図示した。なお、図１、図２において、「■」印は実測値を示し、●印は「計算値」を示す。
表４に示すように、触媒１〜３は、各計算値に対して、「ガソリン」及び「ＬＣＯ」が高収率で得られると共に、「ＨＣＯ」及び「コーク」が低収率となった。また、図１より、触媒組成物Ａ1が１０〜４０質量％の場合（すなわち、ＷA：ＷB＝１０：９０〜４０：６０の場合）に、触媒１のＫ値（Ｋm）が触媒組成物Ａ1のＫ値（ＫA）及び触媒組成物Ｂ1のＫ値（ＫB）よりも高くなっている。図２より、触媒組成物Ａ１が１０〜９０質量％の場合（すなわち、ＷA：ＷB＝１０：９０〜９０：１０の場合）に、触媒１のガソリン収率が触媒組成物Ａ1及び触媒組成物Ｂ1のそれぞれのガソリン収率よりも高くなっている。The K values in Table 4 are shown in FIG. 1, and the gasoline yield is shown in FIG. In FIG. 1 and FIG. 2, “■” indicates an actually measured value, and ● indicates a “calculated value”.
As shown in Table 4, with respect to each of the calculated values, the
但し、
・転化率（質量％）＝（ａ−ｂ）／ａ×１００
ａ：原料油の質量
ｂ：灯軽油留分（ＬＣＯ）及び重質留分（ＨＣＯ）の合計の質量
・Ｋ値＝転化率／（１００−転化率）
・水素（質量％）＝ｃ／ａ×１００
ｃ：生成ガス中の水素の質量
・Ｃ１＋Ｃ２（質量％）＝ｄ／ａ×１００
ｄ：生成ガス中のＣ１（メタン）、Ｃ２（エタン、エチレン）の質量
・ＬＰＧ（液化石油ガス、質量％）＝ｅ／ａ×１００
ｅ：生成ガス中のプロパン、プロピレン、ブタン、及びブチレンの質量
・ガソリン（質量％）＝ｆ／ａ×１００
ｆ：生成油中のガソリン（沸点範囲：Ｃ５(ブタン）の沸点（２０℃）〜２０４℃）の質量
・ＬＣＯ（質量％）＝ｇ／ａ×１００
ｇ：生成油中のライトサイクルオイル（沸点範囲：２０４〜３４３℃）の質量
・ＨＣＯ（質量％）＝ｈ／ａ×１００
ｈ：生成油中のヘビーサイクルオイル（沸点範囲：３４３℃以上）の質量
・コーク（質量％）＝ｉ／ａ×１００
ｉ：触媒混合物上に析出したコーク質量
以下の実施例についても同様である。
《実験例２：Ａ2−Ｂ2》
（実施例４：触媒６）
触媒組成物Ａ2と触媒組成物Ｂ2とを、乾燥基準で質量比が７０：３０となるように混合し、流動接触分解触媒６を調製した。
（実施例５：触媒７）
触媒組成物Ａ2と触媒組成物Ｂ2とを、乾燥基準で質量比が５０：５０となるように混合し、流動接触分解触媒７を調製した。
（実施例６：触媒８）
触媒組成物Ａ2と触媒組成物Ｂ2とを、乾燥基準で質量比が３０：７０となるように混合し、流動接触分解触媒８を調製した。
（比較例３：触媒９）
触媒組成物Ａ2を流動接触分解触媒９とした。
（比較例４：触媒１０）
触媒組成物Ｂ2を流動接触分解触媒１０とした。
（試験例２）
流動接触分解触媒６〜１０について、試験例１と同様に流動接触分解を行った。表５にその反応結果を示す。表５に示すように、触媒６〜８は、各計算値に対して、「ガソリン」及び「ＬＰＧ」が高収率で得られると共に、「ＨＣＯ」及び「コーク」が低収率となった。However,
Conversion (mass%) = (ab) / a × 100
a: Mass of raw material oil
b: Total mass of kerosene oil fraction (LCO) and heavy fraction (HCO) K value = conversion / (100-conversion)
・ Hydrogen (mass%) = c / a × 100
c: Mass of hydrogen in the generated gas C1 + C2 (mass%) = d / a × 100
d: Mass of C1 (methane) and C2 (ethane, ethylene) in the product gas LPG (liquefied petroleum gas, mass%) = e / a × 100
e: Mass of propane, propylene, butane, and butylene in the product gas. Gasoline (mass%) = f / a × 100
f: Mass of gasoline in boiling oil (boiling point range: boiling point of C5 (butane) (20 ° C.) to 204 ° C.) LCO (mass%) = g / a × 100
g: Mass of light cycle oil (boiling point range: 204-343 ° C.) in the product oil HCO (mass%) = h / a × 100
h: Mass of heavy cycle oil (boiling point range: 343 ° C. or higher) in the product oil Coke (mass%) = i / a × 100
i: Coke mass deposited on catalyst mixture The same applies to the following examples.
<< Experimental example 2: A 2 -B 2 >>
(Example 4: Catalyst 6)
Catalyst composition A 2 and catalyst composition B 2 were mixed so that the mass ratio was 70:30 on a dry basis to prepare fluid catalytic cracking catalyst 6.
(Example 5: Catalyst 7)
Catalyst composition A 2 and catalyst composition B 2 were mixed so that the mass ratio was 50:50 on a dry basis to prepare fluid catalytic cracking catalyst 7.
(Example 6: Catalyst 8)
Catalyst composition A 2 and catalyst composition B 2 were mixed so that the mass ratio was 30:70 on a dry basis to prepare fluid catalytic cracking catalyst 8.
(Comparative Example 3: Catalyst 9)
The catalyst composition A 2 was fluid catalytic cracking catalyst 9.
(Comparative Example 4: Catalyst 10)
The catalyst composition B 2 was fluid catalytic cracking
(Test Example 2)
The fluid catalytic cracking catalysts 6 to 10 were subjected to fluid catalytic cracking in the same manner as in Test Example 1. Table 5 shows the reaction results. As shown in Table 5, in the catalysts 6 to 8, “gasoline” and “LPG” were obtained in high yield and “HCO” and “coke” were low in yield for each calculated value. .
《実験例３：Ａ2−Ｂ3》
（実施例７：触媒１１）
触媒組成物Ａ2と触媒組成物Ｂ3とを、乾燥基準で質量比が７０：３０となるように混合し、流動接触分解触媒１１を調製した。
（実施例８：触媒１２）
触媒組成物Ａ2と触媒組成物Ｂ3とを、乾燥基準で質量比が５０：５０となるように混合し、流動接触分解触媒１２を調製した。
（実施例９：触媒１３）
触媒組成物Ａ2と触媒組成物Ｂ3とを、乾燥基準で質量比が３０：７０となるように混合し、流動接触分解触媒１３を調製した。
（比較例５：触媒１４）
触媒組成物Ｂ3を流動接触分解触媒１４とした。
（試験例３）
流動接触分解触媒９及び１１〜１４について、試験例１と同様に流動接触分解を行った。表６にその反応結果を示す。表６に示すように、触媒１１〜１３は、各計算値に対して、「添加率」、「ＬＰＧ」及び「ガソリン」が高収率で得られると共に、「ＨＣＯ」及び「コーク」が低収率となった。<< Experimental Example 3: A 2 -B 3 >>
(Example 7: Catalyst 11)
The catalyst composition A 2 and the catalyst composition B 3 were mixed so that the mass ratio was 70:30 on a dry basis to prepare a fluid catalytic cracking catalyst 11.
(Example 8: Catalyst 12)
Catalyst composition A 2 and catalyst composition B 3 were mixed so that the mass ratio was 50:50 on a dry basis to prepare fluid catalytic cracking catalyst 12.
(Example 9: Catalyst 13)
Catalyst composition A 2 and catalyst composition B 3 were mixed so that the mass ratio was 30:70 on a dry basis to prepare fluid catalytic cracking catalyst 13.
(Comparative Example 5: Catalyst 14)
The catalyst composition B 3 was used as the fluid catalytic cracking catalyst 14.
(Test Example 3)
The fluid catalytic cracking catalysts 9 and 11 to 14 were subjected to fluid catalytic cracking in the same manner as in Test Example 1. Table 6 shows the reaction results. As shown in Table 6, the catalysts 11 to 13 can obtain “addition rate”, “LPG” and “gasoline” in a high yield and low “HCO” and “coke” for each calculated value. Yield.
《実験例４：Ａ2−Ｂ4》
（実施例１０：触媒１５）
触媒組成物Ａ2と触媒組成物Ｂ4とを、乾燥基準で質量比が７０：３０となるように混合し、流動接触分解触媒１５を調製した。
（実施例１１：触媒１６）
触媒組成物Ａ2と触媒組成物Ｂ4とを、乾燥基準で質量比が５０：５０となるように混合し、流動接触分解触媒１６を調製した。
（実施例１２：触媒１７）
触媒組成物Ａ2と触媒組成物Ｂ4とを、乾燥基準で質量比が３０：７０となるように混合し、流動接触分解触媒１７を調製した。
（比較例６：触媒１８）
触媒組成物Ｂ4を流動接触分解触媒１８とした。
（試験例４）
流動接触分解触媒９及び１５〜１８について、試験例１と同様に流動接触分解を行った。表６にその反応結果を示す。表７に示すように、触媒１５〜１７は、各計算値に対して、「添加率」、「ＬＰＧ」及び「ガソリン」が高収率で得られると共に、「水素」、「Ｃ１＋Ｃ２」、「ＬＣＯ」、「ＨＣＯ」及び「コーク」が低収率となった。<< Experimental Example 4: A 2 -B 4 >>
(Example 10: Catalyst 15)
Catalyst composition A 2 and catalyst composition B 4 were mixed so that the mass ratio was 70:30 on a dry basis to prepare fluid catalytic cracking catalyst 15.
(Example 11: Catalyst 16)
Catalyst composition A 2 and catalyst composition B 4 were mixed so that the mass ratio was 50:50 on a dry basis to prepare fluid catalytic cracking catalyst 16.
(Example 12: Catalyst 17)
Catalyst composition A 2 and catalyst composition B 4 were mixed so that the mass ratio was 30:70 on a dry basis to prepare fluid catalytic cracking catalyst 17.
(Comparative Example 6: Catalyst 18)
The catalyst composition B 4 was used as the fluid catalytic cracking catalyst 18.
(Test Example 4)
The fluid catalytic cracking catalysts 9 and 15 to 18 were subjected to fluid catalytic cracking in the same manner as in Test Example 1. Table 6 shows the reaction results. As shown in Table 7, with respect to each calculated value, the catalysts 15 to 17 can obtain “addition rate”, “LPG”, and “gasoline” in high yield, as well as “hydrogen”, “C1 + C2”, “ “LCO”, “HCO” and “Coke” resulted in low yields.
《実験例５：Ａ3−Ｂ2》
（実施例１３：触媒１９）
触媒組成物Ａ3と触媒組成物Ｂ2とを、乾燥基準で質量比が７０：３０となるように混合し、流動接触分解触媒１９を調製した。
（実施例１４：触媒２０）
触媒組成物Ａ3と触媒組成物Ｂ2とを、乾燥基準で質量比が５０：５０となるように混合し、流動接触分解触媒２０を調製した。
（実施例１５：触媒２１）
触媒組成物Ａ3と触媒組成物Ｂ2とを、乾燥基準で質量比が３０：７０となるように混合し、流動接触分解触媒２１を調製した。
（比較例７：触媒２２）
触媒組成物Ａ3を流動接触分解触媒２２とした。
（試験例５）
流動接触分解触媒１０及び１９〜２２について、試験例１と同様に流動接触分解を行った。表８に示すように、触媒１９〜２１は、各計算値に対して、「ガソリン」及び「ＬＣＯ」が高収率で得られると共に、「ＨＣＯ」及び「コーク」が低収率となった。<< Experimental Example 5: A 3 -B 2 >>
(Example 13: Catalyst 19)
Catalyst composition A 3 and catalyst composition B 2 were mixed so that the mass ratio was 70:30 on a dry basis to prepare fluid catalytic cracking catalyst 19.
(Example 14: Catalyst 20)
Catalyst composition A 3 and catalyst composition B 2 were mixed so that the mass ratio was 50:50 on a dry basis to prepare fluid catalytic cracking
(Example 15: Catalyst 21)
Catalyst composition A 3 and catalyst composition B 2 were mixed so that the mass ratio was 30:70 on a dry basis to prepare fluid catalytic cracking catalyst 21.
(Comparative Example 7: Catalyst 22)
The catalyst composition A 3 was used as a fluid catalytic cracking catalyst 22.
(Test Example 5)
The fluid catalytic cracking
《実験例６：Ａ3−Ｂ3》
（比較例１６：触媒２３）
触媒組成物Ａ3と触媒組成物Ｂ3とを、乾燥基準で質量比が７０：３０となるように混合し、流動接触分解触媒２３を調製した。
（実施例１７：触媒２４）
触媒組成物Ａ3と触媒組成物Ｂ3とを、乾燥基準で質量比が５０：５０となるように混合し、流動接触分解触媒２４を調製した。
（実施例１８：触媒２５）
触媒組成物Ａ3と触媒組成物Ｂ3とを、乾燥基準で質量比が３０：７０となるように混合し、流動接触分解触媒２５を調製した。
（試験例６）
流動接触分解触媒１４及び２２と２３〜２５について、試験例１と同様に流動接触分解を行った。表９に反応結果を示す。表９に示すように、触媒２３〜２５は、各計算値に対して、「ガソリン」及び「ＬＣＯ」が高収率で得られると共に、「ＨＣＯ」及び「コーク」が低収率となった。<< Experiment 6: A 3 -B 3 >>
(Comparative Example 16: Catalyst 23)
Catalyst composition A 3 and catalyst composition B 3 were mixed so that the mass ratio was 70:30 on a dry basis to prepare fluid catalytic cracking catalyst 23.
(Example 17: Catalyst 24)
A catalyst composition A 3 and the catalyst composition B 3, the mass ratio on a dry basis are mixed so that the ratio of 50:50 to prepare a fluid catalytic cracking catalyst 24.
(Example 18: Catalyst 25)
Catalyst composition A 3 and catalyst composition B 3 were mixed so that the mass ratio was 30:70 on a dry basis to prepare fluid catalytic cracking catalyst 25.
(Test Example 6)
The fluid catalytic cracking catalysts 14 and 22 and 23 to 25 were subjected to fluid catalytic cracking in the same manner as in Test Example 1. Table 9 shows the reaction results. As shown in Table 9, with respect to each calculated value, the catalysts 23 to 25 obtained “gasoline” and “LCO” in high yield, and “HCO” and “coke” in low yield. .
《実験例７：Ａ3−Ｂ4》
（実施例１９：触媒２６）
触媒組成物Ａ3と触媒組成物Ｂ4とを、乾燥基準で質量比が７０：３０となるように混合し、流動接触分解触媒２６を調製した。
（実施例２０：触媒２７）
触媒組成物Ａ3と触媒組成物Ｂ4とを、乾燥基準で質量比が５０：５０となるように混合し、流動接触分解触媒２７を調製した。
（実施例２１：触媒２８）
触媒組成物Ａ3と触媒組成物Ｂ4とを、乾燥基準で質量比が３０：７０となるように混合し、流動接触分解触媒２８を調製した。
（試験例７）
流動接触分解触媒１８及び２２と２６〜２８について、試験例１と同様に流動接触分解を行った。表１０に反応結果を示す。表１０に示すように、触媒２６〜２８は、各計算値に対して、「ガソリン」及び「ＬＣＯ」が高収率で得られると共に、「ＨＣＯ」及び「コーク」が低収率となった。<< Experimental Example 7: A 3 -B 4 >>
(Example 19: Catalyst 26)
Catalyst composition A 3 and catalyst composition B 4 were mixed so that the mass ratio was 70:30 on a dry basis to prepare fluid catalytic cracking catalyst 26.
(Example 20: Catalyst 27)
Catalyst composition A 3 and catalyst composition B 4 were mixed so that the mass ratio was 50:50 on a dry basis to prepare fluid catalytic cracking catalyst 27.
(Example 21: Catalyst 28)
A catalyst composition A 3 and the catalyst composition B 4, the mass ratio on a dry basis are mixed so that the 30:70, to prepare a fluid catalytic cracking catalyst 28.
(Test Example 7)
The fluid catalytic cracking catalysts 18 and 22 and 26 to 28 were subjected to fluid catalytic cracking in the same manner as in Test Example 1. Table 10 shows the reaction results. As shown in Table 10, in the catalysts 26 to 28, “gasoline” and “LCO” were obtained in high yield and “HCO” and “coke” were low in yield for each calculated value. .
《実験例８：Ａ2−Ａ3》
（比較例８：触媒２９）
触媒組成物Ａ2と触媒組成物Ａ3とを、乾燥基準で質量比が７０：３０となるように混合し、流動接触分解触媒２６を調製した。
（比較例９：触媒３０）
触媒組成物Ａ2と触媒組成物Ａ3とを、乾燥基準で質量比が５０：５０となるように混合し、流動接触分解触媒２７を調製した。
（比較例１０：触媒３１）
触媒組成物Ａ2と触媒組成物Ａ3とを、乾燥基準で質量比が３０：７０となるように混合し、流動接触分解触媒２８を調製した。
（試験例８）
流動接触分解触媒９及び２２と２９〜３１について、試験例１と同様に流動接触分解を行った。表１１に反応結果を示す。表１１に示すように、触媒２９〜３１の「ガソリン」、「ＬＣＯ」、「ＨＣＯ」及び「コーク」の収率は、それぞれの測定値と計算値がほぼ等しくなった。<< Experimental Example 8: A 2 -A 3 >>
(Comparative Example 8: Catalyst 29)
The catalyst composition A 2 and the catalyst composition A 3 were mixed so that the mass ratio was 70:30 on a dry basis to prepare a fluid catalytic cracking catalyst 26.
(Comparative Example 9: Catalyst 30)
Catalyst composition A 2 and catalyst composition A 3 were mixed so that the mass ratio was 50:50 on a dry basis to prepare fluid catalytic cracking catalyst 27.
(Comparative Example 10: Catalyst 31)
The catalyst composition A 2 and the catalyst composition A 3 were mixed so that the mass ratio was 30:70 on a dry basis to prepare a fluid catalytic cracking catalyst 28.
(Test Example 8)
The fluid catalytic cracking catalysts 9 and 22 and 29 to 31 were subjected to fluid catalytic cracking in the same manner as in Test Example 1. Table 11 shows the reaction results. As shown in Table 11, the measured values and the calculated values of the “gasoline”, “LCO”, “HCO”, and “coke” of the catalysts 29 to 31 were almost equal.
《実験例９：Ｂ2−Ｂ3》
（比較例１１：触媒３２）
触媒組成物Ｂ2と触媒組成物Ｂ3とを、乾燥基準で質量比が７０：３０となるように混合し、流動接触分解触媒２６を調製した。
（比較例１２：触媒３３）
触媒組成物Ｂ2と触媒組成物Ｂ3とを、乾燥基準で質量比が５０：５０となるように混合し、流動接触分解触媒２７を調製した。
（比較例１３：触媒３４）
触媒組成物Ｂ2と触媒組成物Ｂ3とを、乾燥基準で質量比が３０：７０となるように混合し、流動接触分解触媒２８を調製した。
（試験例９）
流動接触分解触媒１０及び１４と３２〜３４について、試験例１と同様に流動接触分解を行った。表１２に反応結果を示す。表１２に示すように、触媒３２〜３４の「ガソリン」、「ＬＣＯ」、「ＨＣＯ」及び「コーク」の収率は、それぞれの測定値と計算値がほぼ等しくなった。<< Experimental Example 9: B 2 -B 3 >>
(Comparative Example 11: Catalyst 32)
Catalyst composition B 2 and catalyst composition B 3 were mixed so that the mass ratio was 70:30 on a dry basis to prepare fluid catalytic cracking catalyst 26.
(Comparative Example 12: Catalyst 33)
Catalyst composition B 2 and catalyst composition B 3 were mixed so that the mass ratio was 50:50 on a dry basis to prepare fluid catalytic cracking catalyst 27.
(Comparative Example 13: Catalyst 34)
Catalyst composition B 2 and catalyst composition B 3 were mixed so that the mass ratio was 30:70 on a dry basis to prepare fluid catalytic cracking catalyst 28.
(Test Example 9)
The fluid catalytic cracking
以上、本発明であるシリカ系バインダーを含む触媒組成物Ａと、アルミニウム化合物バインダーを含む触媒組成物Ｂとを、質量比が１０：９０〜９０：１０の範囲内で混合した流動接触分解触媒は、触媒組成物Ａ単独の触媒、触媒組成物Ｂ単独の触媒、及び、２種のシリカ系バインダーを含む触媒組成物を混合した触媒、及び、２種のアルミニウム化合物バインダーを含む触媒組成物を混合した触媒のいずれよりも計算値と比較して「ガソリン」及び「ＬＰＧ」が高収率で得られると共に、「ＨＣＯ」及び「コーク」が低収率となる傾向にある。これは、アルミナ化合物バインダーを含む触媒組成物Ｂに含まれるアルミナが、バナジウムやニッケル等の被毒金属と結合して無毒化することにより、シリカ系バインダーを含む触媒組成物Ａが被毒金属により被毒され難くなり、高ガソリン収率及び低コーク収率を保持したまま、高ガソリン収率及び高軽油留分収率並びに高ボトム分解になると解される。 As described above, the fluid catalytic cracking catalyst in which the catalyst composition A containing the silica-based binder according to the present invention and the catalyst composition B containing the aluminum compound binder are mixed within a mass ratio of 10:90 to 90:10 is obtained. A catalyst comprising a catalyst composition A alone, a catalyst comprising a catalyst composition B alone, a catalyst composition comprising two silica-based binders, and a catalyst composition comprising two aluminum compound binders. Compared to the calculated values of any of the catalysts prepared, “gasoline” and “LPG” are obtained in high yield, and “HCO” and “coke” tend to be in low yield. This is because the alumina contained in the catalyst composition B containing the alumina compound binder is combined with the poisoned metal such as vanadium or nickel to be detoxified, so that the catalyst composition A containing the silica-based binder is made of the poisoned metal. It becomes difficult to be poisoned, and it is understood that high gasoline yield and high light oil fraction yield and high bottom cracking are obtained while maintaining high gasoline yield and low coke yield.
本発明は、前記した実施の形態に限定されるものではなく、本発明の要旨を変更しない範囲での変更は可能であり、例えば、前記したそれぞれの実施の形態や変形例の一部又は全部を組み合わせて本発明の流動接触分解触媒を構成する場合も本発明の権利範囲に含まれる。 The present invention is not limited to the above-described embodiment, and can be changed without changing the gist of the present invention. For example, some or all of the above-described embodiments and modifications are possible. When the fluid catalytic cracking catalyst of the present invention is constituted by combining these, the scope of the right of the present invention is also included.
例えば、前記実施例においては、シリカ系バインダーを含む触媒組成物Ａの１種と、アルミニウム化合物バインダーを含む触媒組成物Ｂの１種を組み合わせて流動接触分解触媒を製造しているが、触媒組成物Ａ及び／又は触媒組成物Ｂを２種以上として組み合わせて流動接触分解触媒を構成してもよい。 For example, in the above embodiment, a fluid catalytic cracking catalyst is produced by combining one type of catalyst composition A containing a silica-based binder and one type of catalyst composition B containing an aluminum compound binder. You may comprise a fluid catalytic cracking catalyst combining the thing A and / or the catalyst composition B as 2 or more types.
Claims (13)
Ｋ＝転化率／（１００−転化率）・・・（１）
なお、転化率は、下記式（２）で示される。
転化率（質量％）＝（ａ−ｂ）／ａ×１００・・・（２）
ここで、ａは原料油の質量、ｂは灯軽油留分及び重質留分の合計の質量である。 And Y-type zeolite and a catalyst composition containing 10 to 30 wt% silica binder as binder A, and a catalyst composition B containing 10 to 30 wt% of the aluminum compound binder as Y-type zeolite and a binder, the catalyst Carbonization characterized in that the mass of composition A is W A and the mass of catalyst composition B is W B , and the mass ratio (W A : W B ) is mixed within the range of 10:90 to 90:10. It is a fluid catalytic cracking catalyst for hydrogen oil, and the catalyst composition A and the catalyst composition B each have a K value represented by the following formula (1) (respective K values are represented by “K A ” and “K B ”): ) Is one or more, a fluid catalytic cracking catalyst for hydrocarbon oils.
K = conversion / (100-conversion) (1)
In addition, a conversion rate is shown by following formula (2).
Conversion (mass%) = (ab) / a × 100 (2)
Here, a is the mass of the raw material oil, and b is the total mass of the kerosene oil fraction and the heavy fraction.
ＫA：ＫB＝１：０．５〜１：１．５・・・（３） 2. The fluid catalytic cracking catalyst for hydrocarbon oil according to claim 1, wherein the K values of the catalyst composition A and the catalyst composition B have a relationship represented by the following formula (3).
K A : K B = 1: 0.5 to 1: 1.5 (3)
（ａ）塩基性塩化アルミニウム。
（ｂ）重リン酸アルミニウム。
（ｃ）アルミナゾル。 The fluid catalytic cracking catalyst for hydrocarbon oil according to any one of claims 1 to 5, wherein the aluminum compound binder is at least one selected from the group consisting of the following (a) to (c).
(A) Basic aluminum chloride.
(B) Aluminum biphosphate.
(C) Alumina sol.
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| JP5499407B2 (en) * | 2010-09-15 | 2014-05-21 | 一般財団法人石油エネルギー技術センター | Method for producing catalytic cracking catalyst |
| JP5445781B2 (en) * | 2010-09-15 | 2014-03-19 | 一般財団法人石油エネルギー技術センター | Method for producing catalytic cracking catalyst |
| JP5470660B2 (en) * | 2010-09-15 | 2014-04-16 | 一般財団法人石油エネルギー技術センター | Method for producing catalytic cracking catalyst |
| JP5940935B2 (en) | 2012-08-17 | 2016-06-29 | 日揮触媒化成株式会社 | Hydrocarbon catalytic cracking catalyst |
| JP6407967B2 (en) | 2014-03-17 | 2018-10-17 | 日揮触媒化成株式会社 | Catalyst test equipment for fluid catalytic cracking |
| JP7512196B2 (en) * | 2017-12-11 | 2024-07-08 | ビーエーエスエフ コーポレーション | Reactive silica-alumina matrix component composition for residual oil cracking catalysts |
| WO2020044859A1 (en) * | 2018-08-29 | 2020-03-05 | 日揮触媒化成株式会社 | Fluid catalytic cracking catalyst for hydrocarbon oil |
| JP7123864B2 (en) * | 2019-02-28 | 2022-08-23 | 日揮触媒化成株式会社 | Fluid catalytic cracking catalyst for hydrocarbon oil |
| US11731114B2 (en) | 2018-08-29 | 2023-08-22 | Jgc Catalysts And Chemicals Ltd. | Fluid catalytic cracking catalyst for hydrocarbon oil |
| WO2024069636A1 (en) | 2022-09-27 | 2024-04-04 | Hindustan Petroleum Corporation Limited | A catalyst composition for catalytic cracking of paraffin rich feed into light olefins |
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| AU582404B2 (en) * | 1984-12-27 | 1989-03-23 | Mobil Oil Corporation | Catalytic cracking with a mixture of faujasite-type zeolites and zeolite beta |
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| US4946814A (en) * | 1989-03-10 | 1990-08-07 | Thiele-Kaolin Company | Process for improving the physical and catalytic properties of fluid cracking catalysts |
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| JPS54156013A (en) * | 1978-05-30 | 1979-12-08 | Shell Int Research | Manufacture of gasoline |
| JPS61157579A (en) * | 1984-12-27 | 1986-07-17 | モ−ビル オイル コ−ポレ−ション | Catalytic cracking of faujasite type zeolite and zeolite beta blend |
| JPS6295384A (en) * | 1985-10-18 | 1987-05-01 | アクゾ・ナ−ムロ−ゼ・フエンノ−トシヤツプ | Method for cracking hydrocarbon stock material |
| JPH06501876A (en) * | 1990-08-06 | 1994-03-03 | シーレ カオリン カンパニー | Method for improving physical properties and catalytic properties of fluidized cracking catalysts |
| JP2004528963A (en) * | 2001-02-21 | 2004-09-24 | アクゾ ノーベル ナムローゼ フェンノートシャップ | Cracking catalyst composition |
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |