JP5426308B2 - Fluid catalytic cracking method - Google Patents
Fluid catalytic cracking method Download PDFInfo
- Publication number
- JP5426308B2 JP5426308B2 JP2009231759A JP2009231759A JP5426308B2 JP 5426308 B2 JP5426308 B2 JP 5426308B2 JP 2009231759 A JP2009231759 A JP 2009231759A JP 2009231759 A JP2009231759 A JP 2009231759A JP 5426308 B2 JP5426308 B2 JP 5426308B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- catalytic cracking
- mass
- fluid catalytic
- zeolite
- 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.)
- Active
Links
- 238000004231 fluid catalytic cracking Methods 0.000 title claims description 47
- 238000000034 method Methods 0.000 title claims description 39
- 239000003054 catalyst Substances 0.000 claims description 198
- 238000004523 catalytic cracking Methods 0.000 claims description 45
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 44
- 229910021536 Zeolite Inorganic materials 0.000 claims description 39
- 239000010457 zeolite Substances 0.000 claims description 39
- 239000002253 acid Substances 0.000 claims description 30
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 17
- 239000002734 clay mineral Substances 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 description 29
- 238000011156 evaluation Methods 0.000 description 24
- 239000003921 oil Substances 0.000 description 18
- 239000000295 fuel oil Substances 0.000 description 16
- 239000002994 raw material Substances 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 238000005336 cracking Methods 0.000 description 10
- 239000000571 coke Substances 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 238000011067 equilibration Methods 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000010025 steaming Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 208000005374 Poisoning Diseases 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 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 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- MOOOZOQCKRBKHM-UHFFFAOYSA-N cyclohexane;vanadium Chemical compound [V].C1CCCCC1 MOOOZOQCKRBKHM-UHFFFAOYSA-N 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
本発明は、流動接触分解方法、特にガソリン留分の収率を高め、コークの生成を抑制し得る流動接触分解方法に関するものである。 The present invention relates to a fluid catalytic cracking method, and more particularly to a fluid catalytic cracking method capable of increasing the yield of a gasoline fraction and suppressing coke formation.
流動接触分解は、重質油と触媒とを接触させて分解し、主としてガソリン留分を製造することを目的としている。
流動接触分解の原料は、通常減圧軽油や常圧残油等の重質油が用いられる。流動接触分解の原料である重質油、特に常圧残油には多量の金属（ニッケルやバナジウムなど）が含まれ、触媒が循環して使用されることにより金属が触媒に堆積する。
The purpose of fluid catalytic cracking is to mainly produce a gasoline fraction by bringing heavy oil and a catalyst into contact for cracking.
As the raw material for fluid catalytic cracking, usually heavy oil such as vacuum gas oil or atmospheric residue is used. Heavy oil, particularly atmospheric residual oil, which is a raw material for fluid catalytic cracking, contains a large amount of metal (such as nickel and vanadium), and the metal is deposited on the catalyst as the catalyst is circulated.
近年では、従来型の流動接触分解（ＦＣＣ）装置に、原料油である減圧軽油に加え、より重質で金属分が多い常圧残油や減圧残油を混合処理したり、残油流動接触分解（ＲＦＣＣ）装置の原料油としてより重質で金属分の多い減圧残油を混合処理するなど、ＦＣＣ装置やＲＦＣＣ装置にとってよりシビアーな状況となっている。
このような状況下で、ＦＣＣ装置やＲＦＣＣ装置での原料油の分解率を維持・向上させる手段として、より分解活性の高い流動接触分解触媒を投入することや、流動接触分解触媒の投入量を増加することが考えられる。しかし、単に触媒活性が高い流動接触分解触媒を増加すると、原料油の過分解が起こり、コーク生成が増加して、ＦＣＣ装置やＲＦＣＣ装置の再生塔の負荷が高くなり、処理量の制約に繋がる結果となる。逆にあまり低い活性の触媒を用いると触媒投入量を多くしなければならないという不具合がある。
In recent years, conventional fluid catalytic cracking (FCC) equipment has been mixed with heavy-pressure, heavy-pressure atmospheric residue and reduced-pressure residue, in addition to reduced-pressure gas oil, which is a feedstock, The situation is more severe for FCC devices and RFCC devices, for example, by mixing and treating a heavier, metal-rich reduced-pressure residue as a raw material oil for a cracking (RFCC) device.
Under such circumstances, as a means for maintaining and improving the cracking rate of the feedstock oil in the FCC device or RFCC device, a fluid catalytic cracking catalyst having higher cracking activity or a loading amount of fluid catalytic cracking catalyst can be set. It is possible to increase. However, if the number of fluid catalytic cracking catalysts with high catalytic activity is simply increased, over-decomposition of feedstock occurs, coke generation increases, the load on the regeneration tower of the FCC unit and RFCC unit increases, and this leads to a restriction on the throughput. Result. On the other hand, if a catalyst with a very low activity is used, there is a problem that the amount of catalyst input must be increased.
ところで、非特許文献１で記述されているように、流動接触分解における新しい触媒は、磨耗による触媒のロスや接触分解活性の維持のために投入されるもので、通常は、流動接触分解装置内の触媒全量に対し１〜２質量％投入されている。また、特許文献１では、流動接触分解に用いる触媒として、分解活性が高い特定の結晶性アルミノ珪酸塩と無機酸化物マトリックスとからなる接触分解触媒を提案している。
しかしながら、もし原料油が重質化したり、あるいは金属分が増加した場合において、単に新しい触媒の投入量を増加したり、分解活性が高い触媒を使用した場合、上記のとおり、初期段階において過分解を生じる結果となり、充分な問題解決には至らない。
このようなことから、原料油が重質化したり、あるいは金属分が増加した場合においても、長期間に亘ってガソリン留分の収率を高く、コークの生成を抑制することができる流動接触分解方法の開発が切望されている。
By the way, as described in Non-Patent Document 1, a new catalyst in fluid catalytic cracking is introduced in order to maintain catalyst loss and catalytic cracking activity due to wear. 1-2 mass% of the total amount of the catalyst. Patent Document 1 proposes a catalytic cracking catalyst comprising a specific crystalline aluminosilicate having a high cracking activity and an inorganic oxide matrix as a catalyst used for fluid catalytic cracking.
However, if the feedstock becomes heavier or the metal content increases, if the amount of new catalyst added is simply increased or if a catalyst with high cracking activity is used, as described above, overcracking occurs in the initial stage. As a result, the problem cannot be solved sufficiently.
For this reason, even when the feedstock becomes heavier or the metal content increases, fluid catalytic cracking can increase the yield of gasoline fraction over a long period of time and suppress coke formation. The development of the method is anxious.
本発明は、このような状況下において、より重質化したり、金属分の含有量が増加した原料油を流動接触分解する場合においても、長期間に亘ってガソリン留分の収率を高く、かつコークの生成を抑制することができ、同時に原料油の分解率を高くすることができる流動接触分解方法を提供することを目的とする。 Under such circumstances, the present invention is capable of increasing the yield of gasoline fraction over a long period of time even when fluidized or cracked feedstock that is heavier or has an increased metal content, And it aims at providing the fluid catalytic cracking method which can suppress the production | generation of coke and can make the decomposition rate of raw material oil high simultaneously.
本発明者らは、鋭意研究を重ねた結果、特定の指標に基づいて、流動接触分解方法において新たに投入される新しい触媒の性状及び該触媒の補充割合を制御することによって、本発明の目的を達成し得ることを見出した。本発明はかかる知見に基づいて完成したものである。 As a result of intensive research, the inventors of the present invention controlled the properties of a new catalyst to be newly introduced in the fluid catalytic cracking method and the replenishment ratio of the catalyst based on a specific index. Found that it can be achieved. The present invention has been completed based on such findings.
すなわち、本発明は、
〔１〕平衡触媒の一部を抜き出して新しい触媒を補充しながら行う流動接触分解方法であって、新しい触媒としてアンモニアＴＰＤ法による酸量が５０〜２５０μｍｏｌ／ｇである触媒を用いるとともに、流動接触分解装置内の触媒全量に対する新しい触媒の１日あたりの補充割合Ａ（質量％）を、当該新しい触媒の酸量Ｂ（μｍｏｌ／ｇ）と、下記の式（Ｉ）を満たすように調整して行うことを特徴とする流動接触分解方法、
７００ ≦ Ａ×Ｂ ≦ １，８００ ・・・・（Ｉ）
〔２〕新しい触媒の１日あたりの補充割合Ａが、流動接触分解装置内の触媒全量に対し４質量％以上である上記〔１〕に記載の流動接触分解方法、
〔３〕前記新しい触媒が、ゼオライトを含有することを特徴とする上記［１］に記載の流動接触分解方法、
〔４〕前記ゼオライトが、Ｙ型ゼオライトまたはベータゼオライトである上記〔３〕に記載の流動接触分解方法、
〔５〕前記Ｙ型ゼオライトが、格子定数（Ｕ．Ｄ．）が２．４３０〜２．４５０ｎｍであることを特徴とする上記〔４〕に記載の流動接触分解方法、
〔６〕前記新しい触媒が、（ａ）ゼオライト１０〜４０質量％、（ｂ）アルミナ２〜３０質量％、（ｃ）粘土鉱物１０〜６０質量％、及び（ｄ）バインダー１０〜３０質量％を含有することを特徴とする上記〔３〕に記載の流動接触分解方法、
を提供するものである。
That is, the present invention
[1] A fluid catalytic cracking method in which a part of an equilibrium catalyst is extracted and replenished with a new catalyst, wherein a catalyst having an acid amount of 50 to 250 μmol / g by ammonia TPD method is used as a new catalyst, and fluid contact The replenishment ratio A (mass%) of the new catalyst per day with respect to the total amount of catalyst in the cracking apparatus is adjusted so as to satisfy the acid amount B (μmol / g) of the new catalyst and the following formula (I). A fluid catalytic cracking method, characterized by
700 ≦ A × B ≦ 1,800 (I)
[2] The fluid catalytic cracking method according to [1], wherein the replenishment ratio A per day of the new catalyst is 4% by mass or more based on the total amount of the catalyst in the fluid catalytic cracking apparatus,
[3] The fluid catalytic cracking method according to [1], wherein the new catalyst contains zeolite.
[4] The fluid catalytic cracking method according to [3], wherein the zeolite is Y-type zeolite or beta zeolite,
[5] The fluid catalytic cracking method according to the above [4], wherein the Y-type zeolite has a lattice constant (UD) of 2.430 to 2.450 nm,
[6] The new catalyst comprises (a) 10-40% by mass of zeolite, (b) 2-30% by mass of alumina, (c) 10-60% by mass of clay mineral, and (d) 10-30% by mass of binder. The fluid catalytic cracking method according to [3] above, characterized by comprising:
Is to provide.
本発明によれば、重質化したり、金属分の含有量が増加した原料油を流動接触分解する場合においても、長期間に亘ってガソリン留分の収率を高く、かつコークの生成を抑制することができ、同時に原料油の分解率を高くすることができる流動接触分解方法を提供することができる。 According to the present invention, the yield of gasoline fraction is increased over a long period and the production of coke is suppressed even when fluidized catalytic cracking of feedstock that has become heavy or has increased metal content. It is possible to provide a fluid catalytic cracking method that can increase the cracking rate of the raw material oil at the same time.
本発明の流動接触分解方法においては、触媒の一部を抜き出して新しい触媒（新触媒）を補充しながら行う。重質油と接触しながら循環使用される触媒（以下、「平衡触媒」と称する。）に、重質油中に存在する金属が堆積して触媒活性が低下するため、触媒全体として接触分解反応におけるガソリン留分の収率を高く維持し、コークの生成を抑制する性能を維持するためである。
前記流動接触分解方法における平衡触媒の一部を抜き出して新しい触媒を補充する場合の補充割合は、下記の式（Ｉ）を満たすように調整することが必要である。
７００ ≦ Ａ×Ｂ ≦ １，８００ ・・・・（Ｉ）
式中、Ａは、流動接触分解装置内の触媒全量に対する新しい触媒の１日あたりの補充割合（質量％）、Ｂは新しい触媒のアンモニアＴＰＤ法による酸量（μｍｏｌ／ｇ）を示す。
式（Ｉ）の〔Ａ×Ｂ〕の値が７００未満では、所望の原料油の分解率やガソリン収率を高く保つことができなくなり、また、〔Ａ×Ｂ〕の値が１，８００を越えると原料油の過分解を起こし、不要なコークを生成することとなり、本発明の目的を達成することができない。従って、〔Ａ×Ｂ〕の値は、８００〜１，６００であることがより好ましい。
In the fluid catalytic cracking method of the present invention, the catalyst is partially extracted and replenished with a new catalyst (new catalyst). Since the catalyst present in heavy oil accumulates on the catalyst that is circulated while in contact with heavy oil (hereinafter referred to as “equilibrium catalyst”), the catalytic activity decreases, so the catalytic cracking reaction as a whole of the catalyst This is to maintain a high yield of gasoline fraction and to suppress the production of coke.
When a part of the equilibrium catalyst in the fluid catalytic cracking method is extracted and a new catalyst is replenished, it is necessary to adjust the replenishment ratio so as to satisfy the following formula (I).
700 ≦ A × B ≦ 1,800 (I)
In the formula, A represents the replenishment rate (mass%) of the new catalyst per day with respect to the total amount of the catalyst in the fluid catalytic cracker, and B represents the acid amount (μmol / g) of the new catalyst according to the ammonia TPD method.
If the value of [A × B] in formula (I) is less than 700, the desired feedstock cracking rate and gasoline yield cannot be kept high, and the value of [A × B] is 1,800. If it exceeds, raw material oil will be excessively decomposed and unnecessary coke will be produced, and the object of the present invention cannot be achieved. Therefore, the value of [A × B] is more preferably 800 to 1,600.
前記新しい触媒は、アンモニアＴＰＤ法による酸量（以下、「酸量」と略称することがある）Ｂが、５０〜２５０μｍｏｌ／ｇのものであることが必要である。新しい触媒のアンモニアＴＰＤ法による酸量Ｂが５０μｍｏｌ／ｇ未満では、触媒の補充割合Ａが過大になることにより経済性に劣るため好ましくなく、また、酸量Ｂが、２５０μｍｏｌ／ｇを越えると、原料重質油の過分解が生ずる恐れがあって好ましくない。したがって新しい触媒は、アンモニアＴＰＤ法による酸量は、８０〜２５０μｍｏｌ／ｇのものであることがより好ましい。 The new catalyst is required to have an acid amount (hereinafter sometimes abbreviated as “acid amount”) B by an ammonia TPD method of 50 to 250 μmol / g. If the acid amount B by the ammonia TPD method of the new catalyst is less than 50 μmol / g, it is not preferable because the replenishment ratio A of the catalyst is excessive, resulting in poor economy. If the acid amount B exceeds 250 μmol / g, There is a risk of overdecomposition of the raw material heavy oil, which is not preferable. Therefore, it is more preferable that the new catalyst has an acid amount by the ammonia TPD method of 80 to 250 μmol / g.
また、前記新しい触媒の１日あたりの補充割合Ａは、４質量％以上であることが好ましい。Ａが４質量％以上であれば、触媒全体の活性低下を確実に抑制する効果が得られる。 The replenishment ratio A per day of the new catalyst is preferably 4% by mass or more. If A is 4 mass% or more, the effect of reliably suppressing the activity fall of the whole catalyst will be acquired.
本発明に用いる新しい触媒としては、上記の酸量を有するとともに、さらに以下の組成を有することが好ましい。すなわち、
（１）ゼオライト（ａ）を含有する触媒であることが好ましい。
すなわち、ゼオライトからなる触媒、若しくはゼオライトと他の成分とを含む触媒が好ましい。
（２）さらに、（ａ）ゼオライトとともに、（ｂ）アルミナを含有する触媒であることが好ましい。
（ａ）と（ｂ）含むことによって触媒の酸量及び細孔分布、全比表面積などを適正に調整することが容易になる。
（３）また、さらに、（ａ）と（ｂ）に加えて、（ｃ）粘土鉱物、及び（ｄ）バインダーを含有することが好ましい。
このことによって、触媒の細孔分布を調整し、また触媒の機械的強度を高めることができる。
以上のことから、（ａ）〜（ｄ）を含む触媒（組成物）が特に好ましい。
The new catalyst used in the present invention preferably has the above-mentioned acid amount and further has the following composition. That is,
(1) A catalyst containing zeolite (a) is preferable.
That is, a catalyst made of zeolite or a catalyst containing zeolite and other components is preferable.
(2) Furthermore, it is preferable that the catalyst contains (a) zeolite together with (a) zeolite.
By including (a) and (b), it becomes easy to properly adjust the acid amount and pore distribution of the catalyst, the total specific surface area, and the like.
(3) Further, in addition to (a) and (b), (c) a clay mineral and (d) a binder are preferably contained.
This can adjust the pore distribution of the catalyst and increase the mechanical strength of the catalyst.
From the above, the catalyst (composition) containing (a) to (d) is particularly preferable.
前記（ａ）成分のゼオライトとしては、重質油の分解に適した細孔分布を有する点でＹ型ゼオライトやベータゼオライトが好ましく、中でも、Ｙ型ゼオライトが好ましい。
Ｙ型ゼオライトとしては、超安定Ｙ型ゼオライト（ＵＳＹ）、ＮａＹやＨＹを希土類で交換したＲＥＹ、及びこれらにスチーミング処理等を施して得られるＲＥＵＳＹが特に好ましい。
また、Ｙ型ゼオライトは、格子定数（Ｕ．Ｄ．）が２．４３０〜２．４５０ｎｍであるＹ型ゼオライトが好ましい。Ｕ．Ｄ．が２．４３０〜２．４５０ｎｍであれば、目的とする酸量を有する触媒（組成物）を容易に得ることができる。
なお、ゼオライトの酸量は、アルカリとのイオン交換、酸処理、スチーミング処理、被毒物質による吸着処理などによって調整することができる。
また、本発明で用いるゼオライトは、さらに全比表面積が３００〜１，０００ｍ2／ｇのものが好ましく、４００〜１，０００ｍ2／ｇのものがより好ましい。全比表面積が３００ｍ2／ｇ以上であれば、所望のガソリン留分の収率が得られる点で好ましく、全比表面積が１，０００ｍ2／ｇ以下であれば原料重質油の過分解が抑制される点で好ましい。
なお、全比表面積は、窒素吸着法のＡＳＴＭ Ｄ４３６５−９５によって測定されるものである。
As the zeolite of the component (a), Y-type zeolite and beta zeolite are preferable because they have a pore distribution suitable for heavy oil decomposition, and Y-type zeolite is particularly preferable.
As the Y-type zeolite, ultra-stable Y-type zeolite (USY), REY obtained by exchanging NaY or HY with rare earth, and REUSY obtained by subjecting them to a steaming treatment are particularly preferable.
The Y-type zeolite is preferably Y-type zeolite having a lattice constant (UD) of 2.430 to 2.450 nm. U. D. If it is 2.430-2.450 nm, the catalyst (composition) which has the target acid amount can be obtained easily.
The acid amount of zeolite can be adjusted by ion exchange with alkali, acid treatment, steaming treatment, adsorption treatment with poisonous substances, and the like.
Further, the zeolite used in the present invention further preferably has a total specific surface area 300~1,000m 2 / g, it is more preferred 400~1,000m 2 / g. If the total specific surface area is 300 m 2 / g or more, it is preferable in that the yield of the desired gasoline fraction is obtained, and if the total specific surface area is 1,000 m 2 / g or less, the raw material heavy oil is excessively decomposed. It is preferable in terms of being suppressed.
The total specific surface area is measured by ASTM D4365-95 of the nitrogen adsorption method.
前記（ｂ）成分であるアルミナとしては、擬ベーマイトが好ましく用いられる。擬ベーマイトを製造するには、硫酸アルミニウム水溶液とアンモニア水、アルミン酸ナトリウム水溶液と硫酸、硝酸等の鉱酸、あるいは硫酸アルミニウム水溶液とアルミン酸ナトリウム水溶液などと組み合わせ、中和反応させ、アルミナゲルを沈殿させ、沈殿したアルミナゲルをろ過及び洗浄してナトリウムイオン、硫酸イオンを除去し、アルミナゲルケーキとする。このアルミナゲルケーキを再びイオン交換水で再スラリー化し、固形分濃度５〜３０質量％とし、スプレードライヤーにて乾燥温度１００〜２５０℃で噴霧乾燥すると、擬ベーマイトが得られる。 Pseudoboehmite is preferably used as the alumina as the component (b). Pseudoboehmite is produced by combining an aqueous solution of aluminum sulfate and aqueous ammonia, an aqueous solution of sodium aluminate and a mineral acid such as sulfuric acid or nitric acid, or an aqueous solution of aluminum sulfate and an aqueous solution of sodium aluminate. The precipitated alumina gel is filtered and washed to remove sodium ions and sulfate ions to obtain an alumina gel cake. When this alumina gel cake is re-slurried with ion-exchanged water to a solid content concentration of 5 to 30% by mass and spray dried with a spray dryer at a drying temperature of 100 to 250 ° C., pseudoboehmite is obtained.
また（ｃ）成分の粘土鉱物としては、カオリンやベントナイトを用いることができる。
さらに、（ｄ）成分のバインダーとしては、シリカゾル、アルミナゾル、シリカ・アルミナゾル等が好ましく用いられる。
As the clay mineral of component (c), kaolin or bentonite can be used.
Further, as the binder of component (d), silica sol, alumina sol, silica / alumina sol and the like are preferably used.
本発明に用いる好ましい触媒としては、さらに必要に応じてシリカ・アルミナを配合することができる。この場合、シリカ・アルミナ中の（シリカ／アルミナ）比は、好ましくは５／９５〜８０／２０（質量／質量）であり、好ましくは１０／９０〜７０／３０（質量／質量）である。シリカの量が多すぎると、シリカ・アルミナの細孔径を大きくすることができなかったり、触媒組成物の細孔分布がブロードとなり、重質油が細孔の中に入れなくなることがある。 As a preferred catalyst used in the present invention, silica / alumina can be further blended as required. In this case, the (silica / alumina) ratio in silica / alumina is preferably 5/95 to 80/20 (mass / mass), and preferably 10/90 to 70/30 (mass / mass). If the amount of silica is too large, the pore diameter of silica / alumina cannot be increased, or the pore distribution of the catalyst composition becomes broad, and heavy oil may not enter the pores.
上記（ａ）〜（ｄ）を含む触媒組成物である場合の各成分の配合割合については、（ａ）成分のゼオライトは好ましくは１０〜４０質量％、更に好ましくは１５〜３５質量％、（ｂ）成分のアルミナは、好ましくは２〜３０質量％、更に好ましくは２〜２０質量％、（ｃ）粘土鉱物は好ましくは１０〜６０質量％、更に好ましくは１５〜５０質量％、（ｄ）バインダーは１０〜３０質量％、好ましくは１５〜２５質量％である。 About the compounding ratio of each component in the case of the catalyst composition containing said (a)-(d), Preferably the zeolite of (a) component is 10-40 mass%, More preferably, it is 15-35 mass%, ( The component b) alumina is preferably 2 to 30% by mass, more preferably 2 to 20% by mass, (c) the clay mineral is preferably 10 to 60% by mass, more preferably 15 to 50% by mass, (d) A binder is 10-30 mass%, Preferably it is 15-25 mass%.
前記（ａ）ゼオライトの含有量が１０質量％以上であれば、ガソリンの収率を高く保つことができ、一方、ゼオライトの含有量が４０質量％以下であれば、ゼオライトの種類を問わず、原料重質油や生成したガソリン留分が過分解を起こし、ガス及びコークの生成が増大する恐れがない。
前記（ｂ）成分のアルミナの含有量が２質量％以上であれば、原料重質油の分解に必要なメソ細孔が確保でき、アルミナの含有量が３０質量％以下であれば原料重質油が大まかに分解した後、ガソリンに更に分解する分解活性点を提供する（ａ）成分（ゼオライト）の必要量を確保することが容易である。
（ｃ）成分の粘土鉱物の含有量が１０質量％以上であればガソリン留分の収率が低下することがなく、６０質量％以下であれば他の触媒の有効成分の配合量を制限する弊害はない。
（ｄ）バインダーの含有量が１０質量％以上であると触媒の機械的強度を確保でき、３０質量％以下であれば他の有効成分の必要な配合量を確保することが容易である。
If the content of the zeolite (a) is 10% by mass or more, the yield of gasoline can be kept high, while if the content of zeolite is 40% by mass or less, regardless of the type of zeolite, There is no fear that the raw material heavy oil or the produced gasoline fraction undergoes overdecomposition and the production of gas and coke increases.
If the alumina content of the component (b) is 2% by mass or more, mesopores necessary for the decomposition of the raw material heavy oil can be secured, and if the alumina content is 30% by mass or less, the raw material heavy It is easy to ensure the required amount of component (zeolite) (a) that provides a decomposition active site that further decomposes into gasoline after the oil is roughly decomposed.
(C) If the content of the component clay mineral is 10% by mass or more, the yield of the gasoline fraction does not decrease, and if it is 60% by mass or less, the blending amount of the active components of other catalysts is limited. There is no evil.
(D) When the binder content is 10% by mass or more, the mechanical strength of the catalyst can be ensured, and when it is 30% by mass or less, it is easy to ensure a necessary blending amount of other active ingredients.
本発明に用いることが好ましい、前記（ａ）〜（ｄ）からなる新しい触媒（組成物）の製造方法としては、例えば、以下の方法が挙げられる。
（ａ）ゼオライト、（ｂ）アルミナ、さらには（ｃ）粘土鉱物及び（ｄ）バインダーを各前記好ましい配合割合の範囲で採取し、それをイオン交換水と混合し、固形分濃度が好ましくは５〜２５質量％のスラリーとする。このとき、アルミナの原料である熱処理擬ベーマイトやゼオライト及び粘土鉱物、は０．２〜５μｍに粉砕しておくことが好ましい。またスラリーはｐＨ３〜９に調整することが好ましい。
続いて、上記により得られたスラリーを、スプレードライヤーにて１００〜４００℃で噴霧乾燥し、好ましくは直径２０〜１５０μｍ、より好ましくは３０〜１２０μｍの球状触媒とする。
次いでこれを８０℃〜２００℃で、０．５〜５時間焼成することにより目的とする流動接触分解触媒が得られる。
なお、必要に応じて、さらに酸量を調整するためにスチーミング等の処理を行ってもよい。
このような方法によって、酸量が５０〜２５０μｍｏｌ／ｇである触媒を得ることができる。
As a method for producing a new catalyst (composition) comprising the above (a) to (d), which is preferably used in the present invention, for example, the following methods can be mentioned.
(A) Zeolite, (b) Alumina, (c) Clay mineral, and (d) Binder are collected in the ranges of the above preferred blending ratios, mixed with ion-exchanged water, and the solids concentration is preferably 5 A slurry of ˜25% by mass is used. At this time, it is preferable that the heat-treated pseudo boehmite, the zeolite, and the clay mineral, which are raw materials of alumina, are pulverized to 0.2 to 5 μm. The slurry is preferably adjusted to pH 3-9.
Subsequently, the slurry obtained as described above is spray-dried at 100 to 400 ° C. with a spray dryer, and preferably a spherical catalyst having a diameter of 20 to 150 μm, more preferably 30 to 120 μm.
Subsequently, the target fluid catalytic cracking catalyst is obtained by baking this at 80 to 200 ° C. for 0.5 to 5 hours.
If necessary, a treatment such as steaming may be performed to further adjust the acid amount.
By such a method, a catalyst having an acid amount of 50 to 250 μmol / g can be obtained.
本発明に用いる好ましい触媒の酸量は、触媒を構成するゼオライト、アルミナをそれぞれスチーミング処理、アルカリイオン交換処理、被毒物質による被毒処理等を行って全体の酸量を調整しても良い。スチーミング処理の場合は、例えば、４００〜６００℃、１〜５時間程度曝せばよく、アルカリイオン交換処理の場合は、例えば、５０〜７０℃の炭酸ナトリウム水溶液に０．５〜３時間入れることなどの条件で行うことができる。 The acid amount of a preferable catalyst used in the present invention may be adjusted by performing a steaming treatment, an alkali ion exchange treatment, a poisoning treatment with a poisoning substance, etc. on the zeolite and alumina constituting the catalyst, respectively. . In the case of a steaming treatment, for example, it may be exposed to 400 to 600 ° C. for about 1 to 5 hours. It can be performed under such conditions.
本発明で好ましく用いる新しい触媒は、上記のとおりであるが、平衡触媒として当初から使用する接触分解触媒についても、上記新しい触媒を用いることが好ましい。 The new catalyst preferably used in the present invention is as described above, but it is also preferable to use the new catalyst for the catalytic cracking catalyst used from the beginning as the equilibrium catalyst.
本発明の接触分解方法において原料として用いる重質油としては、とくに制限はなく、減圧軽油、常圧残油あるいは減圧残油、脱硫重油であってもよく、もちろん未脱硫重質油であるか脱硫重質油であるかを問わない。また、これらの混合油であってもよい。 The heavy oil used as a raw material in the catalytic cracking method of the present invention is not particularly limited, and may be a vacuum gas oil, a normal pressure residual oil, a vacuum residual oil, a desulfurized heavy oil or, of course, an undesulfurized heavy oil. It does not matter whether it is desulfurized heavy oil. Moreover, these mixed oils may be sufficient.
また、接触分解反応の反応条件としては、特に制限はなく、流動床（ＦＣＣ、ＲＦＣＣ）式接触分解装置を用い、従来公知の方法で行うことができる。具体的には例えば、反応温度は好ましくは４５０〜５５０℃で行い、触媒／油比は３〜１０（質量／質量）とすることが好ましい。また、触媒の再生温度は６００〜８５０℃とすることが好ましい。 The reaction conditions for the catalytic cracking reaction are not particularly limited, and can be performed by a conventionally known method using a fluidized bed (FCC, RFCC) type catalytic cracking apparatus. Specifically, for example, the reaction temperature is preferably 450 to 550 ° C., and the catalyst / oil ratio is preferably 3 to 10 (mass / mass). The regeneration temperature of the catalyst is preferably 600 to 850 ° C.
また、例えば、流動接触分解ガス中の有用成分であるプロピレンの選択性を向上させる目的の場合には、上記触媒組成に、さらにＺＳＭ−５やＭＣＭ−２２などのプロピレン選択性の高いゼオライトを添加剤として使用してもよい。この場合、添加剤としての前記ゼオライトの投入量は、通常、触媒全体に対し０．５〜１５質量％である。 In addition, for example, in the case of the purpose of improving the selectivity of propylene which is a useful component in the fluid catalytic cracking gas, a zeolite having high propylene selectivity such as ZSM-5 and MCM-22 is added to the catalyst composition. It may be used as an agent. In this case, the input amount of the zeolite as an additive is usually 0.5 to 15% by mass with respect to the whole catalyst.
次に、本発明を実施例により、さらに詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
実施例１
（１）触媒の調製
（ｉ）新触媒の調製
（ａ）東ソー社製ＨＳＺ−３２０ＮＡＡ（ＮａＹ）をアンモニア水溶液とイオン交換後、５００℃で、３時間焼成し、さらに６５０℃で１時間スチーミング処理して、Ｕ．Ｄ．が２．４５０ｎｍ、酸量が１，０５０μｍｏｌ／ｇのＹ型ゼオライトを得た。
（ｂ）米国ＬＢＲｏｃｈｅ ＣｈｅｍｉｃＢｌｓ社製噴霧乾燥球状擬ベーマイトＶＥＲＳＢＬ２５０を５００℃で３時間焼成し、酸量が４６０μｍｏｌ／ｇの活性アルミナを得た。
（ｃ）粘土鉱物としてカオリンを準備した。さらに
（ｄ）シリカバインダーを準備した。
次いで、（ａ）１８質量％、（ｂ）３質量％、（ｃ）５０質量％及び（ｄ）２９質量％を混合しスラリー化し、続いてスプレードライして、接触分解触媒Ａ１を調製した。接触分解触媒Ａ１（新触媒）の酸量は、２００μｍｏｌ／ｇであった。
（ii）擬似平衡化処理触媒の調整
前記接触分解触媒Ａ１を７７０℃―９８容量％スチーム（窒素バランス）でスチーミング処理し、１３時間水熱処理後、バナジン酸ニッケル、バナジウムのシクロヘキサン溶液を用いて、触媒上にニッケル１，４００質量ｐｐｍ、バナジウム２，８００質量ｐｐｍを含浸し、その後、７３５℃―２０容量％スチーム（窒素バランス）−４時間、更には８５０℃―５容量％スチーム（窒素バランス）−４時間を行った。これを擬似平衡化処理触媒Ａ２と称する。Ａ２（平衡化処理触媒）の酸量は、１０μｍｏｌ／ｇであった。
（iii）反応評価
小型ライザー装置（グレースダビソン社製「ＤＣＲ」）により反応評価を行った。
評価条件：触媒充填量１ｋｇ、そのうち、新触媒である接触分解触媒Ａ１を７０ｇ、前記（ii）の擬似平衡化処理触媒Ａ２を９３０ｇ充填し、反応温度５４５℃、Ｃ／Ｏ＝５．２で、アラビアンヘビー／アラビアンライト＝５０容量％／５０容量％相当品の脱硫重油を原料油として反応評価した。原料油性状を表１に、反応評価結果を表２に示す。
また、表中の新触媒Ａ１は、接触分解触媒Ａ１を６００℃にて２時間焼成したものを用いた。以下の新触媒についても同様である。
Example 1
(1) Preparation of catalyst (i) Preparation of new catalyst (a) HSZ-320NAA (NaY) manufactured by Tosoh Corporation was ion-exchanged with an aqueous ammonia solution, calcined at 500 ° C for 3 hours, and further steamed at 650 ° C for 1 hour. Processed U.P. D. Was 2.450 nm and an acid amount of 1,050 μmol / g was obtained.
(B) Spray-dried spherical pseudoboehmite VERSBL250 manufactured by LBRoche ChemicalBls, USA was calcined at 500 ° C. for 3 hours to obtain activated alumina having an acid amount of 460 μmol / g.
(C) Kaolin was prepared as a clay mineral. Further, (d) a silica binder was prepared.
Next, (a) 18% by mass, (b) 3% by mass, (c) 50% by mass and (d) 29% by mass were mixed and slurried, followed by spray drying to prepare catalytic cracking catalyst A1. The acid amount of the catalytic cracking catalyst A1 (new catalyst) was 200 μmol / g.
(Ii) Preparation of quasi-equilibrium treatment catalyst The catalytic cracking catalyst A1 was steamed at 770 ° C-98% by volume steam (nitrogen balance), hydrothermally treated for 13 hours, and then using a vanadate nickel and vanadium cyclohexane solution. The catalyst was impregnated with 1,400 mass ppm of nickel and 2,800 mass ppm of vanadium, and then 735 ° C.-20 volume% steam (nitrogen balance) -4 hours, and further 850 ° C.-5 volume% steam (nitrogen balance). ) -4 hours. This is referred to as pseudo-equilibrium treatment catalyst A2. The acid amount of A2 (equilibration treatment catalyst) was 10 μmol / g.
(Iii) Reaction Evaluation Reaction evaluation was performed with a small riser device (“DCR” manufactured by Grace Davison).
Evaluation conditions: 1 kg of catalyst charge, of which 70 g of catalytic cracking catalyst A1, which is a new catalyst, and 930 g of quasi-equilibrium treatment catalyst A2 of (ii) above, are charged at a reaction temperature of 545 ° C. and C / O = 5.2. Arabian heavy / Arabian light = 50 vol% / 50 vol% equivalent desulfurized heavy oil was used as a raw material for reaction evaluation. The raw material oil properties are shown in Table 1, and the reaction evaluation results are shown in Table 2.
The new catalyst A1 in the table was obtained by calcining the catalytic cracking catalyst A1 at 600 ° C. for 2 hours. The same applies to the following new catalysts.
実施例２
触媒充填量１ｋｇのうち、新触媒である接触分解触媒Ａ１を４０ｇ、擬似平衡化処理触媒Ａ２を９６０ｇとしたこと以外は、実施例１と同様の方法で反応評価した。結果を表２に示す。
Example 2
The reaction was evaluated in the same manner as in Example 1 except that 40 g of the catalytic cracking catalyst A1 as a new catalyst and 960 g of the quasi-equilibrium treatment catalyst A2 were used in 1 kg of the catalyst charge. The results are shown in Table 2.
実施例３
（ｉ）新触媒の調製
（ａ）東ソー社製ＨＳＺ−３２０ＮＡＡをアンモニア水溶液とイオン交換後、５００℃で、３時間焼成し、さらに６５０℃で６時間スチーミング処理して、Ｕ．Ｄ．が２．４４０ｎｍ、酸量が１，０５０μｍｏｌ／ｇのＹ型ゼオライトを得た。
（ｂ）〜（ｄ）は実施例１と同じものを用意した。
次いで、（ａ）２２質量％、（ｂ）３質量％、（ｃ）５０質量％及び（ｄ）２５質量％をスラリー化し、次いでスプレードライして、接触分解触媒Ｂ１を調製した。接触分解触媒Ｂ１（新触媒）の酸量は、１６０μｍｏｌ／ｇであった。
（ii）擬似平衡化処理触媒の調整
接触分解触媒Ｂ１について、実施例１と同様の方法と条件で擬似平衡化処理触媒Ｂ２を調整した。平衡化処理触媒Ｂ２の酸量は、１０μｍｏｌ／ｇであった。
（iii）反応評価
評価条件として、触媒充填量１ｋｇ、そのうち、新触媒である接触分解触媒Ｂ１を１００ｇ、前記（ii）の擬似平衡化処理触媒Ｂ２を９００ｇ充填したこと以外は、実施例１と同様の条件で小型ライザー装置（グレースダビソン社製 「ＤＣＲ」）による反応評価を行った。結果を表３に示す。
Example 3
(I) Preparation of new catalyst (a) HSZ-320NAA manufactured by Tosoh Corporation was ion-exchanged with an aqueous ammonia solution, calcined at 500 ° C. for 3 hours, and further steamed at 650 ° C. for 6 hours. D. Was 2.440 nm and the acid amount was 1,050 μmol / g.
(B)-(d) prepared the same thing as Example 1. FIG.
Next, (a) 22% by mass, (b) 3% by mass, (c) 50% by mass and (d) 25% by mass were slurried and then spray-dried to prepare catalytic cracking catalyst B1. The acid amount of the catalytic cracking catalyst B1 (new catalyst) was 160 μmol / g.
(Ii) Adjustment of quasi-equilibrium treatment catalyst For the catalytic cracking catalyst B1, quasi-equilibrium treatment catalyst B2 was prepared by the same method and conditions as in Example 1. The acid amount of the equilibration catalyst B2 was 10 μmol / g.
(Iii) Reaction Evaluation As the evaluation conditions, Example 1 was used except that 1 kg of the catalyst was charged, of which 100 g of the catalytic cracking catalyst B1 as a new catalyst and 900 g of the pseudo-equilibrium treatment catalyst B2 of (ii) were charged. The reaction was evaluated using a small riser device (“DCR” manufactured by Grace Davison) under the same conditions. The results are shown in Table 3.
実施例４
実施例３で調製した接触分解触媒Ｂ１と、擬似平衡化処理した擬似平衡化処理触媒Ｂ２を用い、評価条件として触媒充填量１ｋｇ、そのうち、新触媒である接触分解触媒Ｂ１の割合を７０ｇ、上記擬似平衡化処理触媒Ｂ２を９３０ｇとしたこと以外は、実施例１と同様の条件で小型ライザー装置（グレースダビソン社製「ＤＣＲ」）による反応評価を行った。結果を表３に示す。
Example 4
Using the catalytic cracking catalyst B1 prepared in Example 3 and the pseudo-equilibrium-treated catalyst B2 subjected to the pseudo-equilibrium treatment, the amount of the catalyst charged is 1 kg as an evaluation condition, and the ratio of the catalytic cracking catalyst B1 as a new catalyst is 70 g. The reaction was evaluated by a small riser device (“DCR” manufactured by Grace Davison) under the same conditions as in Example 1 except that the pseudo-equilibration treatment catalyst B2 was changed to 930 g. The results are shown in Table 3.
実施例５
（ｉ）新触媒及び擬似平衡化処理触媒の調製
（ａ）として、東ソー社製ＨＳＺ−３２０ＮＡＡをアンモニア水溶液とイオン交換後、５００℃で３時間焼成し、さらに６５０℃で２４時間スチーミング処理して、得られたＵ．Ｄ．が２．４３０ｎｍ、酸量が５００μｍｏｌ／ｇのＹ型ゼオライトを用いたこと以外は、実施例１と同様方法で、接触分解触媒Ｃ１及び擬似平衡化処理触媒Ｃ２を調整した。接触分解触媒Ｃ１の酸量は、９０μｍｏｌ／ｇであった。
（ii）反応評価
評価条件として、触媒充填量１ｋｇ、そのうち、新触媒である接触分解触媒Ｃ１を１００ｇ、前記（ii）の擬似平衡化処理触媒Ｃ２を９００ｇ充填したこと以外は、実施例１と同様の条件で小型ライザー装置（グレースダビソン社製「ＤＣＲ」）による反応評価を行った。結果を表５に示す。
Example 5
(I) As preparation (a) of a new catalyst and a pseudo-equilibrium treatment catalyst, HSZ-320NAA manufactured by Tosoh Corporation was ion-exchanged with an aqueous ammonia solution, calcined at 500 ° C. for 3 hours, and further steamed at 650 ° C. for 24 hours. U. D. The catalytic cracking catalyst C1 and the quasi-equilibrium treatment catalyst C2 were prepared in the same manner as in Example 1 except that Y-type zeolite having an acid amount of 2.430 nm and an acid amount of 500 μmol / g was used. The acid amount of the catalytic cracking catalyst C1 was 90 μmol / g.
(Ii) Reaction evaluation As the evaluation conditions, Example 1 was used except that 1 kg of the catalyst was charged, of which 100 g of the catalytic cracking catalyst C1 as a new catalyst and 900 g of the pseudo-equilibrium treatment catalyst C2 of (ii) were charged. The reaction was evaluated using a small riser device (“DCR” manufactured by Grace Davison) under the same conditions. The results are shown in Table 5.
比較例１
実施例１で調製した接触分解触媒Ａ１と、擬似平衡化処理した擬似平衡化処理触媒Ａ２を用いて、評価条件として触媒充填量１ｋｇ、そのうち、新触媒である接触分解触媒Ａ１を割合が１００ｇ、擬似平衡化処理触媒Ａ２を９００ｇとしたこと以外は、実施例１と同様の条件で小型ライザー装置（グレースダビソン社製「ＤＣＲ」）による反応評価を行った。結果を表２に示す。
Comparative Example 1
Using the catalytic cracking catalyst A1 prepared in Example 1 and the pseudo-equilibrium-treated catalyst A2 subjected to the pseudo-equilibrium treatment, the amount of the catalyst is 1 kg as an evaluation condition, of which the catalytic cracking catalyst A1 which is a new catalyst has a ratio of 100 g, The reaction was evaluated by a small riser device (“DCR” manufactured by Grace Davison) under the same conditions as in Example 1 except that 900 g of the quasi-equilibrium treatment catalyst A2 was used. The results are shown in Table 2.
比較例２
実施例１で調製した接触分解触媒Ａ１と、擬似平衡化処理した擬似平衡化処理触媒Ａ２を用いて、評価条件として触媒充填量１ｋｇ、そのうち、新触媒である接触分解触媒Ａ１を割合が１０ｇ、擬似平衡化処理触媒Ａ２を９９０ｇとしたこと以外は、実施例１と同様の条件で小型ライザー装置（グレースダビソン社製「ＤＣＲ」）による反応評価を行った。結果を表２に示す。
Comparative Example 2
Using the catalytic cracking catalyst A1 prepared in Example 1 and the pseudo-equilibrium-treated catalyst A2 subjected to the quasi-equilibrium treatment, the catalyst filling amount is 1 kg, of which the catalytic cracking catalyst A1 which is a new catalyst has a ratio of 10 g, The reaction was evaluated by a small riser device (“DCR” manufactured by Grace Davison) under the same conditions as in Example 1 except that the pseudo-equilibration treatment catalyst A2 was changed to 990 g. The results are shown in Table 2.
比較例３
実施例３で調製した接触分解触媒Ｂ１と、擬似平衡化処理した擬似平衡化処理触媒Ｂ２を用いて、評価条件として触媒充填量１ｋｇ、そのうち、新触媒である接触分解触媒Ｂ１を割合が４０ｇ、擬似平衡化処理触媒Ｂ２を９６０ｇとしたこと以外は、実施例１と同様の条件で小型ライザー装置（グレースダビソン社製「ＤＣＲ」）による反応評価を行った。結果を表３に示す。
Comparative Example 3
Using the catalytic cracking catalyst B1 prepared in Example 3 and the pseudo-equilibrium-treated catalyst B2 subjected to the pseudo-equilibrium treatment, the amount of the catalyst is 1 kg as an evaluation condition, of which the catalytic cracking catalyst B1 which is a new catalyst has a ratio of 40 g, A reaction evaluation using a small riser device (“DCR” manufactured by Grace Davison) was performed under the same conditions as in Example 1 except that 960 g of the pseudo-equilibrium treatment catalyst B2 was used. The results are shown in Table 3.
比較例４
実施例３で調製した接触分解触媒Ｂ１と、擬似平衡化処理した擬似平衡化処理触媒Ｂ２を用いて、評価条件として触媒充填量１ｋｇ、そのうち、新触媒である接触分解触媒Ｂ１を割合が１０ｇ、擬似平衡化処理触媒Ｂ２を９９０ｇとしたこと以外は、実施例１と同様の条件で小型ライザー装置（グレースダビソン社製「ＤＣＲ」）による反応評価を行った。結果を表３に示す。
Comparative Example 4
Using the catalytic cracking catalyst B1 prepared in Example 3 and the pseudo-equilibrium-treated catalyst B2 subjected to the pseudo-equilibrium treatment, the amount of the catalyst is 1 kg as an evaluation condition, of which the catalytic cracking catalyst B1 which is a new catalyst has a ratio of 10 g, The reaction was evaluated by a small riser device (“DCR” manufactured by Grace Davison) under the same conditions as in Example 1 except that quasi-equilibrium treatment catalyst B2 was changed to 990 g. The results are shown in Table 3.
比較例５
（ｉ）新触媒及び擬似平衡化処理触媒の調製
（ａ）として、東ソー社製ＨＳＺ−３２０ＮＡＡをアンモニア水溶液とイオン交換後、５００℃で、３時間焼成し、さらに６５０℃で０．２時間スチーミング処理して、得られたＵ．Ｄ．が２．４５６ｎｍ、酸量が２，１００μｍｏｌ／ｇのＹ型ゼオライトを用いたこと以外は、実施例１と同様方法で、接触分解触媒Ｄ１及擬似平衡化処理触媒Ｄ２を調整した。接触分解触媒Ｄ１の酸量は、２６０μｍｏｌ／ｇであった。
（ii）反応評価
評価条件として、触媒充填量１ｋｇ、そのうち、新触媒である接触分解触媒Ｄ１を１００ｇ、擬似平衡化処理触媒Ｄ２を９００ｇ充填したこと以外は、実施例１と同様の条件で小型ライザー装置（グレースダビソン社製「ＤＣＲ」）による反応評価を行った。結果を表４に示す。
Comparative Example 5
(I) Preparation of new catalyst and pseudo-equilibrium treatment catalyst As (a), HSZ-320NAA manufactured by Tosoh Corporation was ion-exchanged with an aqueous ammonia solution, calcined at 500 ° C. for 3 hours, and further at 650 ° C. for 0.2 hour. The U.C. obtained by the teaming process. D. The catalytic cracking catalyst D1 and the quasi-equilibrium treatment catalyst D2 were prepared in the same manner as in Example 1 except that Y-type zeolite having 2.456 nm and an acid amount of 2,100 μmol / g was used. The acid amount of the catalytic cracking catalyst D1 was 260 μmol / g.
(Ii) Reaction evaluation As an evaluation condition, a small amount of the catalyst was charged under the same conditions as in Example 1 except that 1 kg of the catalyst was charged, of which 100 g of the catalytic cracking catalyst D1 as a new catalyst and 900 g of the pseudo-equilibrium treatment catalyst D2 were charged. Reaction evaluation with a riser device (“DCR” manufactured by Grace Davison) was performed. The results are shown in Table 4.
比較例６
比較例５で調製した接触分解触媒Ｄ１と、擬似平衡化処理した擬似平衡化処理触媒Ｄ２を用いて、小型ライザー装置（グレースダビソン社製「ＤＣＲ」）による反応評価を行った。
評価条件：触媒充填量１ｋｇ、そのうち、新触媒である接触分解触媒Ｄ１の割合が７０ｇ、残りが上記擬似平衡化処理触媒Ｄ２が９３０ｇであって、その他の条件は実施例１と同様の条件にて行った。結果を表４に示す。
Comparative Example 6
Using the catalytic cracking catalyst D1 prepared in Comparative Example 5 and the pseudo-equilibrium-treated catalyst D2 subjected to the pseudo-equilibrium treatment, reaction evaluation was performed using a small riser device (“DCR” manufactured by Grace Davison).
Evaluation conditions: 1 kg of catalyst charge, of which the ratio of the catalytic cracking catalyst D1 which is a new catalyst is 70 g, the rest is 930 g of the pseudo-equilibrium treatment catalyst D2, and the other conditions are the same as in Example 1. I went. The results are shown in Table 4.
比較例７
比較例５で調製した接触分解触媒Ｄ１と、擬似平衡化処理した擬似平衡化処理触媒Ｄ２を用い、評価条件として、触媒充填量１ｋｇ、そのうち、新触媒である接触分解触媒Ｄ１の割合を１０ｇ、擬似平衡化処理触媒Ｄ２を９９０ｇ充填したこと以外は、実施例１と同様の条件で小型ライザー装置（グレースダビソン社製「ＤＣＲ」）による反応評価を行った。結果を表４に示す。
Comparative Example 7
Using the catalytic cracking catalyst D1 prepared in Comparative Example 5 and the pseudo-equilibrium-treated catalyst D2 subjected to the pseudo-equilibrium treatment, the evaluation condition is 1 kg of the catalyst filling amount, of which the ratio of the catalytic cracking catalyst D1 being a new catalyst is 10 g, A reaction evaluation using a small riser device (“DCR” manufactured by Grace Davison) was performed under the same conditions as in Example 1 except that 990 g of the pseudo-equilibrium treatment catalyst D2 was charged. The results are shown in Table 4.
比較例８
実施例５で調製した接触分解触媒Ｃ１と、擬似平衡化処理した擬似平衡化処理触媒Ｃ２を用い、評価条件として、触媒充填量１ｋｇ、そのうち、新触媒である接触分解触媒Ｃ１を７０ｇ、擬似平衡化処理触媒Ｃ２を９３０ｇ充填したこと以外は、実施例１と同様の条件で小型ライザー装置（グレースダビソン社製「ＤＣＲ」）による反応評価を行った。結果を表５に示す。
Comparative Example 8
Using the catalytic cracking catalyst C1 prepared in Example 5 and the pseudo-equilibrium-treated catalyst C2 subjected to the pseudo-equilibrium treatment, the evaluation condition is 1 kg of the catalyst filling amount, 70 g of the catalytic cracking catalyst C1 being the new catalyst, pseudo-equilibrium The reaction was evaluated using a small riser device (“DCR” manufactured by Grace Davison) under the same conditions as in Example 1 except that 930 g of the chemical conversion catalyst C2 was charged. The results are shown in Table 5.
比較例９
実施例５で調製した接触分解触媒Ｃ１と、擬似平衡化処理した擬似平衡化処理触媒Ｃ２を用い、評価条件として触媒充填量１ｋｇ、そのうち、新触媒である接触分解触媒Ｃ１を４０ｇ、平衡化処理触媒Ｃ２を９６０ｇ充填したこと以外は、実施例１と同様の条件で小型ライザー装置（グレースダビソン社製「ＤＣＲ」）による反応評価を行った。結果を表５に示す。
Comparative Example 9
Using the catalytic cracking catalyst C1 prepared in Example 5 and the pseudo-equilibrium-treated catalyst C2 subjected to the quasi-equilibrium treatment, the catalyst filling amount is 1 kg, of which 40 g of the catalytic cracking catalyst C1, which is a new catalyst, is equilibrated. The reaction was evaluated by a small riser device (“DCR” manufactured by Grace Davison) under the same conditions as in Example 1 except that 960 g of catalyst C2 was charged. The results are shown in Table 5.
比較例１０
実施例５で調製した接触分解触媒Ｃ１と、擬似平衡化処理した擬似平衡化処理触媒Ｃ２を用いて、評価条件として、触媒充填量１ｋｇ、そのうち、新触媒である接触分解触媒Ｃ１を１０ｇ、擬似平衡化処理触媒Ｃ２を９９０ｇ充填したこと以外は、実施例１と同様の条件で小型ライザー装置（グレースダビソン社製「ＤＣＲ」）による反応評価を行った。結果を表５に示す。
Comparative Example 10
Using the catalytic cracking catalyst C1 prepared in Example 5 and the pseudo-equilibrium-treated catalyst C2 subjected to the quasi-equilibrium treatment, as an evaluation condition, the catalyst filling amount is 1 kg, of which 10 g of the catalytic cracking catalyst C1 which is a new catalyst is simulated. The reaction was evaluated by a small riser device (“DCR” manufactured by Grace Davison) under the same conditions as in Example 1 except that 990 g of the equilibration catalyst C2 was charged. The results are shown in Table 5.
［注］
表２中の「原油の分解率」は、小型ライザー装置（グレースダビソン社製「ＤＣＲ」）による反応評価において、通油した原料油１００質量％から、流動接触分解反応により生成した流動接触分解残油（ＣＬＯ）の質量％を引いた値である。表３〜５における「原油の分解率」も同様である。
[note]
The "crude oil decomposition rate" in Table 2 indicates the fluid catalytic cracking residue generated by fluid catalytic cracking reaction from 100% by mass of the feedstock oil in the reaction evaluation by a small riser device ("DCR" manufactured by Grace Davison). It is a value obtained by subtracting the mass% of oil (CLO). The same applies to “decomposition rate of crude oil” in Tables 3 to 5.
表２〜５より、本願発明の流動接触分解法では、原料油の分解率が９１．９質量％以上、ガソリン収率が４０．７質量％以上、かつコーク収率は７．３質量％以下であって、いずれも良好であって許容できる範囲にあることが分る（実施例１〜５）。
これに対し、本願発明の要件、〔Ａ×Ｂ〕が低く６４０以下である場合は、ガソリン収率は高いものの原料油の分解率が９１．８質量％以下と低く（比較例２〜４、７〜１０）、本願発明の要件〔Ａ×Ｂ〕が高く２，０００以上の場合は、ガソリン収率が４０．５質量％以下と低く、いずれも好ましくない（比較例１，５，６）。
From Tables 2 to 5, in the fluid catalytic cracking method of the present invention, the cracking rate of the raw material oil is 91.9% by mass or more, the gasoline yield is 40.7% by mass or more, and the coke yield is 7.3% by mass or less. It can be seen that both are good and in an acceptable range (Examples 1 to 5).
On the other hand, when the requirement of the present invention, [A × B] is low and 640 or less, the gasoline yield is high, but the decomposition rate of the feedstock is as low as 91.8% by mass or less (Comparative Examples 2 to 4, 7-10) When the requirement [A × B] of the present invention is high and 2,000 or more, the gasoline yield is as low as 40.5% by mass or less, which is not preferable (Comparative Examples 1, 5, and 6). .
本発明の流動接触分解方法は、重質化したり、金属分の含有量が増加した原料油を流動接触分解する場合においても、長期間に亘ってガソリン留分の収率を高く、かつコークの生成を抑制することができ、同時に原料油の分解率を高くすることができる。したがって、有用な流動接触分解方法として広く利用することができる。 In the fluid catalytic cracking method of the present invention, the yield of gasoline fraction is increased over a long period of time, even in the case of fluid catalytic cracking of feedstock that has become heavy or has an increased metal content. Generation | occurrence | production can be suppressed and the decomposition rate of feedstock can be made high simultaneously. Therefore, it can be widely used as a useful fluid catalytic cracking method.
Claims (6)
７００ ≦ Ａ×Ｂ ≦ １，８００ ・・・・（Ｉ） A fluid catalytic cracking method in which a part of an equilibrium catalyst is extracted and replenished with a new catalyst, wherein a catalyst having an acid amount of 50 to 250 μmol / g according to the ammonia TPD method is used as a new catalyst, The replenishment ratio A (mass%) of the new catalyst per day with respect to the total amount of the catalyst is adjusted so as to satisfy the acid amount B (μmol / g) of the new catalyst and the following formula (I). A fluidized catalytic cracking method.
700 ≦ A × B ≦ 1,800 (I)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009231759A JP5426308B2 (en) | 2009-10-05 | 2009-10-05 | Fluid catalytic cracking method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009231759A JP5426308B2 (en) | 2009-10-05 | 2009-10-05 | Fluid catalytic cracking method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2011079909A JP2011079909A (en) | 2011-04-21 |
| JP5426308B2 true JP5426308B2 (en) | 2014-02-26 |
Family
ID=44074298
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009231759A Active JP5426308B2 (en) | 2009-10-05 | 2009-10-05 | Fluid catalytic cracking method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5426308B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5851031B2 (en) | 2011-07-21 | 2016-02-03 | リライアンス、インダストリーズ、リミテッドＲｅｌｉａｎｃｅ Ｉｎｄｕｓｔｒｉｅｓ Ｌｉｍｉｔｅｄ | Catalyst additive in fluid catalytic cracking (FCC) and its production method |
| CN105562120B (en) * | 2014-10-16 | 2018-09-28 | 中国石油化工股份有限公司 | A kind of Cracking catalyst in batches plus agent, continuous ageing method |
| JP7108570B2 (en) * | 2019-04-01 | 2022-07-28 | 出光興産株式会社 | Method for producing fluid catalytic cracking gasoline |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56157486A (en) * | 1980-05-07 | 1981-12-04 | Nippon Oil Co Ltd | Fluid catalytic cracking process |
| JPH1085603A (en) * | 1996-09-11 | 1998-04-07 | Catalysts & Chem Ind Co Ltd | Catalyst composition for catalytic cracking of hydrocarbon oil and method for catalytically cracking hydrocarbon oil with the same |
| JP3920966B2 (en) * | 1997-06-06 | 2007-05-30 | 東燃ゼネラル石油株式会社 | Additive catalyst for heavy oil cracking |
| US7153413B2 (en) * | 2001-07-10 | 2006-12-26 | W.R. Grace &Co.-Conn. | Gasoline sulfur reduction in fluid catalytic cracking |
| JP4535929B2 (en) * | 2005-04-28 | 2010-09-01 | 財団法人石油産業活性化センター | Catalyst for catalytic cracking of hydrocarbon oil and catalytic cracking method |
| JP2009202153A (en) * | 2008-02-01 | 2009-09-10 | Idemitsu Kosan Co Ltd | Catalyst for catalytic cracking |
-
2009
- 2009-10-05 JP JP2009231759A patent/JP5426308B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2011079909A (en) | 2011-04-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI554604B (en) | Catalytic cracking catalyst includes modified Y zeolite and preparation method thereof | |
| TWI523688B (en) | A method of reducing the sulfur content of a catalytically cracked petro leum fraction and a fluid catalytic cracking process | |
| JP5628027B2 (en) | Fluid catalytic cracking catalyst of hydrocarbon oil and fluid catalytic cracking method of hydrocarbon oil using the same | |
| ES2959237T3 (en) | FCC catalyst compositions containing boron phosphorus oxide | |
| US9415380B2 (en) | Method for manufacturing catalytic cracking catalyst for hydrocarbon oil | |
| EP3868711A1 (en) | Mfi structure molecular sieve rich in mesopore, preparation method therefor, and catalyst containing same and application thereof | |
| CN109304207B (en) | Catalytic cracking catalyst for cracking coker gas oil and preparation method thereof | |
| JP5431167B2 (en) | Catalytic cracking catalyst composition having improved bottoms conversion | |
| WO2014027537A1 (en) | Catalyst for hydrocarbon catalytic cracking | |
| US8940156B2 (en) | Thermochemical structuring of matrix components for FCC catalysts | |
| JP2006142273A (en) | Process for producing catalyst composition for hydrocarbon fluid catalytic cracking | |
| JP5426308B2 (en) | Fluid catalytic cracking method | |
| JP7046763B2 (en) | Fluid cracking catalyst for hydrocarbon oil | |
| EP2874744B1 (en) | Method to prepare MAGNESIUM STABILIZED ULTRA LOW SODA CRACKING CATALYSTS | |
| JPH08173816A (en) | Catalyst composition for fluidized catalytic cracking of hydrocarbon and its production | |
| CN109304222B (en) | Catalytic cracking catalyst for cracking coking wax oil to produce more liquefied gas and preparation method thereof | |
| JP2013111528A (en) | Hydrocarbon catalytic cracking catalyst and method for manufacturing the same | |
| JP6327709B2 (en) | Hydrocarbon oil catalytic cracking catalyst and hydrocarbon oil catalytic cracking method | |
| JP7178829B2 (en) | Fluid catalytic cracking catalyst for hydrocarbon oil | |
| JP2009542428A (en) | Catalyst combined with aluminum sulfate | |
| JP6059944B2 (en) | Method for producing modified zeolite and method for producing catalyst for catalytic cracking of hydrocarbon | |
| RU2800606C2 (en) | Molecular sieve having mfi structure and high mesopore content, method for its production, catalyst containing it and its application | |
| WO2014192070A1 (en) | Catalyst for catalytic cracking of hydrocarbon, and process for producing same | |
| KR20210066930A (en) | Mesopore-rich MFI structure molecular sieve, method for preparing same, catalyst containing same, and use thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20120614 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20130628 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130709 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20131112 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20131128 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 5426308 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |