JP2020169235A - Manufacturing method of fluid catalytic cracking gasoline - Google Patents
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Abstract
Description
本発明は、流動接触分解ガソリンの製造方法に関する。 The present invention relates to a method for producing fluid cracking gasoline.
環境問題に対する意識の高まりに伴い流動接触分解ガソリン等の流動接触分解装置（ＦＣＣ装置）から得られる各種留分中の硫黄分の低減が求められるようになっている。当該硫黄分の低減手法としては、流動接触分解ガソリン中の硫黄分を下げるには、所望のレベルに脱硫した原料油を用いる、または流動接触分解ガソリン留分を水素化や吸着でさらに脱硫する、流動接触分解装置で用いられる脱硫触媒（ＦＣＣ触媒）の開発及び改良による方法などが一般的である。例えば、バナジウムを高含量で含むアルミナ、シリカ等の無機酸化物を担体とする触媒をＦＣＣ触媒として用いて流動接触分解した石油留分の硫黄含量を低減させる方法（例えば、特許文献１参照）、酸化物マトリックス内に分散したゼオライト等に、Ｎｉ、Ｃｕ等の所定の金属種を含む化合物を担持した触媒を用いて、硫黄分を減少させた流動接触分解ガソリンを製造する方法（例えば、特許文献２参照）等が提案されている。しかし、これらの方法では、流動接触分解ガソリンの収率が十分ではないといった問題があった。 With increasing awareness of environmental issues, it is required to reduce the sulfur content in various fractions obtained from a fluid cracking cracker (FCC apparatus) such as gasoline cracking gasoline. As a method for reducing the sulfur content, in order to reduce the sulfur content in the fluid cracked gasoline, a raw material oil desulfurized to a desired level is used, or the fluid catalytic cracked gasoline fraction is further desulfurized by hydrogenation or adsorption. A method by developing and improving a desulfurization catalyst (FCC catalyst) used in a flow catalytic cracking apparatus is common. For example, a method of reducing the sulfur content of petroleum cracks cracked by fluid catalytic cracking using a catalyst using an inorganic oxide such as alumina or silica containing a high content of vanadium as a carrier as an FCC catalyst (see, for example, Patent Document 1). A method for producing a fluid cracking gasoline having a reduced sulfur content by using a catalyst in which a compound containing a predetermined metal species such as Ni and Cu is supported on zeolite or the like dispersed in an oxide matrix (for example, Patent Documents). 2) etc. have been proposed. However, these methods have a problem that the yield of liquid cracking gasoline is not sufficient.
流動接触分解ガソリンの収率の向上、留分中の硫黄分の含有量の低減を目的として、バナジウム、ニッケルの蓄積量を所定の範囲内とし、ゼオライトを含有する触媒を用いることで、低硫黄分流動接触分解ガソリンを製造する方法が提案されている（例えば、特許文献３参照）。 For the purpose of improving the yield of fluid cracking gasoline and reducing the sulfur content in the fraction, the accumulated amount of vanadium and nickel is kept within a predetermined range, and a catalyst containing zeolite is used to reduce sulfur. A method for producing a fractionated catalytic cracking gasoline has been proposed (see, for example, Patent Document 3).
ところで近年、環境問題に対する意識の高まりは増すばかりであり、環境に関する規制は年々厳しくなっている。また、需要者のコストに対する要求も年々厳しくなっており、環境に関する規制を満足するだけでなく、より安価に流動接触分解ガソリンを提供する必要が生じており、その収率の向上が求められている。そのため、特許文献３で開示される流動接触分解ガソリンを製造する方法より、更なる改良が求められている。 By the way, in recent years, awareness of environmental issues has only increased, and environmental regulations have become stricter year by year. In addition, the demands on the cost of consumers are becoming stricter year by year, and it is necessary not only to satisfy the environmental regulations but also to provide liquid cracking gasoline at a lower cost, and it is required to improve the yield. There is. Therefore, further improvement is required from the method for producing fluid cracking gasoline disclosed in Patent Document 3.
そこで、本発明は、流動接触分解ガソリンを収率よく製造し得る、流動接触分解ガソリンの製造方法を提供することを目的とする。 Therefore, an object of the present invention is to provide a method for producing a fluid cracking gasoline, which can produce a fluid cracking gasoline in a high yield.
本発明者らは、前記課題を解決するために鋭意研究を重ねた結果、下記の発明により解決できることを見出した。すなわち本発明は、下記の構成を有する流動接触分解ガソリンの製造方法を提供するものである。 As a result of intensive studies to solve the above problems, the present inventors have found that the following inventions can solve the problems. That is, the present invention provides a method for producing a fluid cracking gasoline having the following constitution.
１．少なくとも脱硫重油を含む原料油を供給する、流動接触分解触媒を投入しながら用いる流動接触分解装置において、その流動接触分解触媒の投入量に対する該原料油中のバナジウム相当金属量を０．４質量％以上４．０質量％以下とすることで、装置内流動接触分解触媒の残留炭素分を０．０５質量％超０．５０質量％以下とする、流動接触分解ガソリンの製造方法。
２．前記バナジウム相当金属量を０．４質量％超２．５質量％以下とする上記１に記載の流動接触分解ガソリンの製造方法。
３．前記流動接触分解装置における再生塔の運転温度が、６１５℃以上６４５℃以下である上記１又は２に記載の流動接触分解ガソリンの製造方法。
４．前記原料油中の重質軽油の含有量が、１０容量％以上９０容量％以下である上記１〜３のいずれか１に記載の流動接触分解ガソリンの製造方法。
1. 1. In a fluid cracking apparatus used while charging a fluid cracking catalyst that supplies at least a raw material oil containing desulfurized heavy oil, the amount of vanadium-equivalent metal in the raw material oil is 0.4% by mass with respect to the amount of the fluid cracking catalyst charged. A method for producing fluid catalytic cracking gasoline, wherein the residual carbon content of the fluid cracking catalyst in the apparatus is more than 0.05 mass% and 0.50 mass% or less by setting the content to 4.0% by mass or less.
2. The method for producing fluid catalytic cracking gasoline according to 1 above, wherein the amount of the vanadium-equivalent metal is more than 0.4% by mass and 2.5% by mass or less.
3. 3. The method for producing fluid catalytic cracking gasoline according to 1 or 2 above, wherein the operating temperature of the regeneration tower in the fluid catalytic cracking apparatus is 615 ° C. or higher and 645 ° C. or lower.
4. The method for producing fluidly cracked gasoline according to any one of 1 to 3 above, wherein the content of heavy light oil in the raw material oil is 10% by volume or more and 90% by volume or less.
本発明によれば、流動接触分解ガソリンを収率よく製造し得る、流動接触分解ガソリンの製造方法を提供することができる。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a method for producing a fluid catalytic cracking gasoline capable of producing a fluid cracking gasoline in a high yield.
〔流動接触分解ガソリンの製造方法〕
本発明における実施形態（以後、単に本実施形態と称する場合がある。）に係る流動接触分解ガソリンの製造方法は、少なくとも脱硫重油を含む原料油を供給する、流動接触分解触媒を投入しながら用いる流動接触分解装置において、当該流動接触分解触媒の投入量に対する該原料油中のバナジウム相当金属量を０．４質量％以上４．０質量％以下とすることで、装置内流動接触分解触媒の残留炭素分を０．０５質量％超０．５０質量％以下とすることを特徴とするものである。
[Manufacturing method of fluid cracking gasoline]
The method for producing a fluid cracking gasoline according to an embodiment of the present invention (hereinafter, may be simply referred to as the present embodiment) is used while feeding a fluid cracking catalyst that supplies at least a raw material oil containing desulfurized heavy oil. In the flow catalytic cracking apparatus, by setting the amount of vanadium-equivalent metal in the raw material oil to 0.4% by mass or more and 4.0% by mass or less with respect to the input amount of the fluid cracking catalyst, the residual fluid catalytic cracking catalyst in the apparatus remains. It is characterized in that the carbon content is more than 0.05% by mass and 0.50% by mass or less.
本実施形態では、流動接触分解触媒の投入量に対する原料油中のバナジウム相当金属量を所定の範囲内とすることで、投入する流動接触分解触媒及び装置内流動接触分解触媒（以下、「平衡触媒」とも称する。）上での原料油の過分解を抑制し、かつ該触媒のバナジウム等の被毒金属種による活性の低下を抑制することができ、結果として流動接触分解ガソリンの収率を向上させることができる。より具体的には、流動接触分解装置に供給する原料油中のバナジウム相当金属量を制御することにより、装置内接触分解触媒（平衡触媒）を所定のバナジウム相当金属量とするとともに、該触媒（平衡触媒）の残留炭素分を制御することができるので、流動接触分解ガソリンの収率を向上させることができる。 In the present embodiment, the amount of vanadium-equivalent metal in the raw material oil is set within a predetermined range with respect to the input amount of the fluidized catalytic cracking catalyst, so that the fluidized cracking catalyst to be charged and the fluidized catalytic cracking catalyst in the apparatus (hereinafter, “equilibrium catalyst”). It is possible to suppress the overcracking of the raw material oil on the above, and to suppress the decrease in activity of the catalyst due to poisonous metal species such as vanadium, and as a result, the yield of liquid cracked gasoline is improved. Can be made to. More specifically, by controlling the amount of vanadium-equivalent metal in the raw material oil supplied to the fluid cracking apparatus, the in-equipment catalytic cracking catalyst (equilibrium catalyst) is set to a predetermined vanadium-equivalent metal amount, and the catalyst ( Since the residual carbon content of the equilibrium catalyst) can be controlled, the yield of cracked cracked gasoline can be improved.
流動接触分解装置で用いられる流動接触分解触媒は、当該装置内の反応塔に固定されるものではなく反応塔内を流動しながら原料油と流動接触することで、原料油の分解反応による流動接触分解ガソリンの生成を促進している。そのため、流動接触分解触媒は、流動接触分解ガソリン及び生成ガス等とともに、その一部は流動接触分解装置外に流出することとなる。また、流動接触分解装置で用いられる流動接触分解触媒は、原料油の分解反応及び触媒再生処理を繰り返して用いられることから、劣化する。そのため、その一部を一定量流動接触分解装置外に抜き出して、新触媒を投入することが一般的に行われており、新触媒を常時補充することとなる。本実施形態の流動接触分解ガソリンの製造方法では、該新触媒の投入量及び原料油の供給量を調整することで、装置内接触分解触媒（平衡触媒）を所定のバナジウム相当金属量とするとともに、該触媒（平衡触媒）の残留炭素分を制御することにより、流動接触分解ガソリンの収率を向上させることができる。 The fluid catalytic cracking catalyst used in the fluid catalytic cracking apparatus is not fixed to the reaction tower in the apparatus, but is in fluid contact with the raw material oil while flowing in the reaction tower, so that the fluid contact is caused by the cracking reaction of the raw material oil. It promotes the production of cracked gasoline. Therefore, a part of the fluidized catalytic cracking catalyst flows out of the fluidized cracking apparatus together with the fluidized catalytic cracking gasoline and the generated gas. Further, the fluid catalytic cracking catalyst used in the fluid catalytic cracking apparatus deteriorates because the cracking reaction of the raw material oil and the catalyst regeneration treatment are repeatedly used. Therefore, it is generally practiced to take out a part of it to the outside of the fluidized catalytic cracking apparatus and add a new catalyst, and the new catalyst is constantly replenished. In the method for producing fluid cracking gasoline of the present embodiment, by adjusting the input amount of the new catalyst and the supply amount of the raw material oil, the in-device catalytic cracking catalyst (equilibrium catalyst) is set to a predetermined vanadium-equivalent metal amount. By controlling the residual carbon content of the catalyst (equilibrium catalyst), the yield of cracked cracked gasoline can be improved.
（原料油）
本実施形態の流動接触分解ガソリンの製造方法において用いられる原料油は、少なくとも脱硫重油を含むものである。
脱硫重油は、重油直接脱硫装置（「ＲＨ装置」とも称する。）で水素化脱硫処理して得られる重油留分（「ＤＳＡＲ」とも称する。）である。重油直接脱硫装置（ＲＨ装置）は、通常、常圧蒸留装置、減圧蒸留装置に接続され、これらの装置から得られる残油（重油）を触媒により水素化脱硫処理する装置である。この装置では、水素化脱硫及び水素化分解が行われ、得られる反応生成物は、気液分離され、液相は蒸留等の分離操作により、ナフサ留分、軽油留分、重油留分等の所望の留分に分留され、回収される。ここで回収される重油留分が、脱硫重油（ＤＳＡＲ）である。
(Ingredient oil)
The raw material oil used in the method for producing fluidly cracked gasoline of the present embodiment contains at least desulfurized heavy oil.
The desulfurized heavy oil is a heavy oil fraction (also referred to as “DSAR”) obtained by hydrodesulfurization treatment with a heavy oil direct desulfurization apparatus (also referred to as “RH apparatus”). The heavy oil direct desulfurization apparatus (RH apparatus) is an apparatus that is usually connected to an atmospheric distillation apparatus and a vacuum distillation apparatus and hydrodesulfurizes the residual oil (heavy oil) obtained from these apparatus with a catalyst. In this device, hydrodesulfurization and hydrocracking are performed, the resulting reaction products are gas-liquid separated, and the liquid phase is separated by distillation or other separation operations to produce naphtha fractions, gas oil fractions, heavy oil fractions, etc. It is fractionated into the desired fraction and recovered. The heavy oil fraction recovered here is desulfurized heavy oil (DSAR).
ＲＨ装置で処理される重油としては特に制限なく、例えば、原油の常圧蒸留残油（ＡＲ）、減圧蒸留残油（ＶＲ）、重質サイクル油（ＨＣＯ：Ｈｅａｖｙ Ｃｙｃｌｅ Ｏｉｌ）、流動接触分解残油（ＣＬＯ：Ｃｌａｒｉｆｉｅｄ Ｏｉｌ）、重質軽油、ビスブレーキング油、ビチューメン等の高密度の石油留分が挙げられ、これらは単独であっても、又は複数種が組み合わされていてもよい。 The heavy oil processed by the RH device is not particularly limited, and for example, crude oil atmospheric distillation residual oil (AR), vacuum distillation residual oil (VR), heavy cycle oil (HCO: Heavy Cycle Oil), and fluid contact decomposition residue. High-density petroleum distillates such as oil (CLO: Clarified Oil), heavy gas oil, bisbraking oil, bitumen and the like can be mentioned, and these may be used alone or in combination of two or more.
ＲＨ装置における水素化脱硫及び水素化分解は、通常触媒の存在下で行われ、反応温度、反応圧力、液空間速度等の各種反応条件を調整することにより、所望の脱硫率、重油の分解率を達成することができる。水素化脱硫及び水素化分解は、特に制限されないが、通常３００〜４５０℃の反応温度で、通常１０〜２２ＭＰａの水素加圧下で行われ、液空間速度（ＬＨＳＶ）は通常０．１〜１０ｈ−１とし、水素／重油比は通常２００〜１０，０００Ｎｍ３／ｋＬである。 Hydrodesulfurization and hydrocracking in the RH apparatus are usually performed in the presence of a catalyst, and by adjusting various reaction conditions such as reaction temperature, reaction pressure, and liquid space velocity, the desired desulfurization rate and the decomposition rate of heavy oil Can be achieved. Hydrodesulfurization and hydrocracking is not particularly limited, at a reaction temperature of usually 300 to 450 ° C., carried out at a hydrogen pressure of usually 10～22MPa, the liquid hourly space velocity (LHSV) is usually 0.1 to 10 - Set to 1 , the hydrogen / heavy oil ratio is usually 200 to 10,000 Nm 3 / kL.
原料油には、脱硫重油以外の留分が含まれていてもよい。そのような留分としては特に制限はなく、例えば、原油の常圧蒸留、減圧蒸留により得られる重質軽油（ＨＧＯ）、減圧軽油（ＶＧＯ）、これらの重質軽油及び減圧軽油等を間接脱硫装置で脱硫処理して得られる脱硫減圧軽油（ＶＨＨＧＯ）、間接脱硫重油と溶剤脱れき装置から得られる脱れき油（ＤＡＯ）、減圧重油（ＶＲ）、コーカーガスオイル、コーカーボトム油等の各種重質油が挙げられる。中でも、重質軽油（ＨＧＯ）、減圧軽油（ＶＧＯ）が好ましく、重質軽油（ＨＧＯ）が含まれることがより好ましい。 The raw material oil may contain a fraction other than desulfurized heavy oil. Such a distillate is not particularly limited, and for example, heavy gas oil (HGO), vacuum gas oil (VGO) obtained by atmospheric distillation of crude oil and vacuum distillation, these heavy gas oil, vacuum gas oil and the like are indirectly desulfurized. Various weights such as desulfurized reduced pressure gas oil (VHHGO) obtained by desulfurization in the equipment, indirect desalted heavy oil and degassed oil (DAO) obtained from the solvent removing equipment, reduced pressure heavy oil (VR), coker gas oil, coker bottom oil, etc. Diesel oil can be mentioned. Among them, heavy light oil (HGO) and reduced pressure light oil (VGO) are preferable, and heavy light oil (HGO) is more preferable.
原料油中の脱硫重油の含有量は、特に制限はないが、好ましくは１０容量％以上、より好ましくは２０容量％以上、より好ましくは３０容量％以上であり、上限として好ましくは９０容量％以下、より好ましくは７５容量％以下、更に好ましくは５０容量％以下である。
原料油中の脱硫重油以外の留分の含有量は、特に制限はないが、好ましくは１０容量％以上、より好ましくは２５容量％以上、更に好ましくは５０容量％以上であり、上限として好ましくは９０容量％以下、より好ましくは８０容量％以下、更に好ましくは７０容量％以下である。
原料油中の脱硫重油、脱硫重油以外の留分の含有量が上記範囲内であると、流動接触分解触媒の投入量に対する原料油中のバナジウム相当金属量を所定範囲内としやすくなり、また後述するように再生塔における運転温度を通常より低くして流動接触分解触媒の水熱熱劣化を抑制しながら該触媒上の残留炭素分の低減を図ることができ、結果として流動接触分解ガソリンの収率の向上を図ることができる。
The content of desulfurized heavy oil in the raw material oil is not particularly limited, but is preferably 10% by volume or more, more preferably 20% by volume or more, more preferably 30% by volume or more, and the upper limit is preferably 90% by volume or less. , More preferably 75% by volume or less, still more preferably 50% by volume or less.
The content of the fraction other than the desulfurized heavy oil in the raw material oil is not particularly limited, but is preferably 10% by volume or more, more preferably 25% by volume or more, still more preferably 50% by volume or more, and is preferably an upper limit. It is 90% by volume or less, more preferably 80% by volume or less, still more preferably 70% by volume or less.
When the content of the desulfurized heavy oil and the distillate other than the desulfurized heavy oil in the raw material oil is within the above range, the amount of vanadium-equivalent metal in the raw material oil with respect to the input amount of the fluidized cracking catalyst tends to be within the predetermined range, and will be described later. As a result, the operating temperature in the regeneration tower can be lowered below the normal level to suppress hydrothermal deterioration of the fluid cracking catalyst and the residual carbon content on the catalyst can be reduced. The rate can be improved.
流動接触分解触媒の投入量に対する原料油中のバナジウム相当金属量は、０．４質量％以上４．０質量％以下であることを要する。ここで、流動接触分解触媒の投入量は、流動接触分解装置への新触媒の投入量のことであり、またバナジウム相当金属量（Ｖｅｑ、質量ｐｐｍ）とは、原料油中のバナジウムの含有量（Ｖ、質量ｐｐｍ）及びニッケルの含有量（Ｎｉ、質量ｐｐｍ）を用いた、以下の式で表される数値である。
Ｖｅｑ＝Ｖ＋１／４×Ｎｉ
The amount of vanadium-equivalent metal in the raw material oil with respect to the input amount of the fluid catalytic cracking catalyst needs to be 0.4% by mass or more and 4.0% by mass or less. Here, the amount of the fluidized catalytic cracking catalyst charged is the amount of the new catalyst charged into the fluidized cracking apparatus, and the amount of vanadium-equivalent metal (Veq, mass ppm) is the content of vanadium in the raw material oil. It is a numerical value expressed by the following formula using (V, mass ppm) and nickel content (Ni, mass ppm).
Veq = V + 1/4 x Ni
流動接触分解触媒の投入量に対する原料油中のバナジウム相当金属量が０．４質量％未満であると、原料油の過分解が進行するため、流動接触分解ガソリンの収率が低下する。一方、当該金属量が４．０質量％超であると、流動接触分解触媒がバナジウム等の被毒金属で覆われてしまい、活性が低下するともに、該触媒の再生時に該被毒金属により水熱熱劣化及び破壊が生じる。流動接触分解ガソリンの収率を向上させ、かつ触媒の活性の低下、水熱熱劣化及び破壊を防止する観点から、流動接触分解触媒の投入量に対する原料油中のバナジウム相当金属量は、好ましくは０．４質量％超、より好ましくは０．６質量％以上、更に好ましくは１．０質量％以上であり、上限として好ましくは２．５質量％以下、より好ましくは２．０質量％以下、更に好ましくは１．７質量％以下である。 If the amount of vanadium-equivalent metal in the raw material oil is less than 0.4% by mass with respect to the input amount of the liquid catalytic cracking catalyst, overdecomposition of the raw material oil proceeds, so that the yield of the fluid cracking gasoline decreases. On the other hand, if the amount of the metal exceeds 4.0% by mass, the fluidized cracking catalyst is covered with a poisonous metal such as vanadium, the activity is lowered, and water is generated by the poisoned metal when the catalyst is regenerated. Thermal deterioration and destruction occur. From the viewpoint of improving the yield of fluid cracking cracking gasoline and preventing deterioration of catalyst activity, hydrothermal deterioration and destruction, the amount of vanadium-equivalent metal in the raw material oil with respect to the input amount of the fluid cracking catalyst is preferably. More than 0.4% by mass, more preferably 0.6% by mass or more, still more preferably 1.0% by mass or more, and the upper limit is preferably 2.5% by mass or less, more preferably 2.0% by mass or less. More preferably, it is 1.7% by mass or less.
本実施形態の流動接触分解ガソリンの製造方法において、流動接触分解触媒の投入量に対する原料油中のバナジウム相当金属量は、流動接触分解触媒の投入量の調整、流動接触分解処理装置への原料油の供給量の調整により制御することができ、より容易に制御する観点から、原料油の調整により行うことが好ましい。 In the method for producing fluid cracking gasoline of the present embodiment, the amount of vanadium-equivalent metal in the raw material oil with respect to the input amount of the fluid cracking catalyst is adjusted by adjusting the input amount of the fluid catalytic cracking catalyst and the raw material oil to the fluid cracking treatment apparatus. It can be controlled by adjusting the supply amount of the feedstock, and from the viewpoint of easier control, it is preferable to adjust the feedstock oil.
本実施形態の流動接触分解ガソリンの製造方法において、装置内流動接触分解触媒（平衡触媒）は、０．０５質量％超０．５０質量％以下であることを要する。残留炭素分が０．５０質量％超となると、装置内流動接触分解触媒（平衡触媒）が残留炭素で覆われる、また装置内流動接触分解触媒（平衡触媒）の例えばゼオライト等の担体がコーキングを生じることにより、触媒の活性の低下が生じ、流動接触分解ガソリンの収率が低下する。触媒の活性の低下を抑制し、かつ過分解を抑制し、流動接触ガソリンの収率を向上させる観点から、装置内流動接触分解触媒（平衡触媒）の残留炭素分は、好ましくは０．１質量％以上、より好ましくは０．２質量％以上であり、上限として好ましくは０．５質量％未満、より好ましくは０．４５質量％以下、更に好ましくは０．４質量％以下である。
本明細書において、流動接触分解触媒の残留炭素分は、炭素・硫黄分析装置（例えば、「ＥＭＩＡ−９２０Ｖ２（型番）」、株式会社堀場製作所製）により測定した数値である。
In the method for producing fluid cracking gasoline of the present embodiment, the fluid cracking catalyst (equilibrium catalyst) in the apparatus is required to be more than 0.05% by mass and 0.50% by mass or less. When the residual carbon content exceeds 0.50% by mass, the fluidized catalytic cracking catalyst (equilibrium catalyst) in the apparatus is covered with residual carbon, and the carrier of the fluidized catalytic cracking catalyst (equilibrium catalyst) in the apparatus such as zeolite causes coking. As a result, the activity of the catalyst is lowered, and the yield of cracked cracked gasoline is lowered. From the viewpoint of suppressing a decrease in catalyst activity, suppressing overdecomposition, and improving the yield of fluidized catalytic cracking catalyst (equilibrium catalyst), the residual carbon content of the fluidized catalytic cracking catalyst (equilibrium catalyst) in the apparatus is preferably 0.1 mass by mass. % Or more, more preferably 0.2% by mass or more, and the upper limit is preferably less than 0.5% by mass, more preferably 0.45% by mass or less, still more preferably 0.4% by mass or less.
In the present specification, the residual carbon content of the fluid catalytic cracking catalyst is a numerical value measured by a carbon / sulfur analyzer (for example, "EMIA-920V2 (model number)", manufactured by HORIBA, Ltd.).
また、装置内流動接触分解触媒のバナジウム相当金属量は、好ましくは８００質量ｐｐｍ以上、より好ましくは１５００質量ｐｐｍ以上、更に好ましくは２５００質量ｐｐｍ以上、より更に好ましくは３０００質量ｐｐｍ以上であり、上限として好ましくは５０００質量ｐｐｍ以下、より好ましくは４５００質量ｐｐｍ以下である。上記範囲内であると、触媒の活性の低下を抑制し、流動接触分解ガソリンの収率を向上させることができる。
本明細書において、流動接触分解触媒上のバナジウム相当金属量は、ＡＳＴＭ Ｄ７０８５−０４：Ｓｔａｎｄａｒｄ Ｇｕｉｄｅ ｆｏｒ Ｄｅｔｅｒｍｉｎａｔｉｏｎ ｏｆ Ｃｈｅｍｉｃａｌ Ｅｌｅｍｅｎｔｓ ｉｎ Ｆｌｕｉｄ Ｃａｔａｌｙｔｉｃ Ｃｒａｃｋｉｎｇ Ｃａｔａｌｙｓｔｓ ｂｙ Ｘ−ｒａｙ Ｆｌｕｏｒｅｓｃｅｎｃｅ Ｓｐｅｃｔｒｏｍｅｔｒｙ（ＸＲＦ）に基づき算出される値とする。
The amount of vanadium-equivalent metal of the flow-contact decomposition catalyst in the apparatus is preferably 800 mass ppm or more, more preferably 1500 mass ppm or more, further preferably 2500 mass ppm or more, still more preferably 3000 mass ppm or more, and the upper limit is It is preferably 5000 mass ppm or less, and more preferably 4500 mass ppm or less. Within the above range, it is possible to suppress a decrease in the activity of the catalyst and improve the yield of cracked gasoline.
In the present specification, the amount of vanadium-equivalent metal on the fluidized catalytic cracking catalyst is calculated based on ASTM D7085-04: Standard Guide for Determination of Chemical Elements in Fluid Catalytic Cracking Catalysts by X-ray Fluorescence. To do.
本実施形態で用いられる流動接触分解装置は、通常製油所に設けられる流動接触分解装置と称される装置であれば特に制限なく適用可能である。例えば、流動接触分解装置は、サイクロン、分解生成物排出ライン、ストリッパー、スペント触媒トランスファーライン及びライザー等を有し、原料油の流動接触分解が行われる反応塔と、エアブロワー、エアグリッド、サイクロン、再生触媒トランスファーライン及び排ガスライン等を有し、触媒の再生を行う再生塔と、を備える装置である。 The fluid catalytic cracking apparatus used in the present embodiment can be applied without particular limitation as long as it is an apparatus called a fluid cracking cracker usually provided in a refinery. For example, the fluidized catalytic cracking apparatus includes a cyclone, a decomposition product discharge line, a stripper, a spendt catalyst transfer line, a riser, etc., and a reaction tower in which the raw oil is subjected to fluid cracking, and an air blower, an air grid, a cyclone, etc. It is a device having a regeneration catalyst transfer line, an exhaust gas line, and the like, and equipped with a regeneration tower for regenerating the catalyst.
反応塔では、ライザー内で原料油の分解反応により生成した分解生成物はサイクロンに供給され、サイクロンでは遠心力を利用して分解生成物と流動接触分解触媒とを分離し、分解生成物は分解生成物排出ラインより反応塔から排出され、流動接触分解触媒はスチームが供給されるストリッパーで該触媒上の炭化水素を除去してからスペント触媒トランスファーラインより反応塔から排出され、再生塔に移送される。 In the reaction tower, the cracking product produced by the cracking reaction of the raw material oil in the riser is supplied to the cyclone, and in the cyclone, the cracking product and the fluidized catalytic cracking catalyst are separated by using centrifugal force, and the cracking product is decomposed. It is discharged from the reaction column from the product discharge line, and the fluid catalytic cracking catalyst is discharged from the reaction tower from the spent catalyst transfer line after removing the hydrocarbons on the catalyst with a stripper supplied with steam, and transferred to the regeneration tower. To.
再生塔では、エアブロワーからエアグリッドを経由して再生塔内に供給される空気と、スペント触媒トランスファーラインから再生塔に供給される反応塔で使用された流動接触分解触媒とを接触させて、該触媒上の炭化水素（「コーク」とも称する。）を燃焼させることにより、流動接触分解触媒が再生される。再生された流動接触分解触媒（「再生触媒」とも称する。）と、コークの燃焼により生じた排ガスとはサイクロンで分離され、再生触媒は再生触媒トランスファーラインより再生塔から排出され、ライザーに供給される。一方、排ガスは排ガスラインから再生塔から排出される。 In the regeneration tower, the air supplied from the air blower to the regeneration tower via the air grid is brought into contact with the flow catalytic cracking catalyst used in the reaction tower supplied from the spent catalyst transfer line to the regeneration tower. The flow catalytic cracking catalyst is regenerated by burning the hydrocarbons (also referred to as "corks") on the catalyst. The regenerated fluid cracking catalyst (also referred to as "regeneration catalyst") and the exhaust gas generated by the combustion of cork are separated by a cyclone, and the regeneration catalyst is discharged from the regeneration tower from the regeneration catalyst transfer line and supplied to the riser. To. On the other hand, the exhaust gas is discharged from the regeneration tower from the exhaust gas line.
反応塔の運転条件としては、反応塔の出口温度として、好ましくは４５０℃以上、より好ましくは４７０℃以上、更に好ましくは４９０℃以上であり、上限として好ましくは５５０℃以下、より好ましくは５４０℃以下、更に好ましくは５３０℃以下である。このような反応条件とすると、分解反応の進行がより促進され、また流動接触分解触媒上の非蒸発の炭化水素をより低減することができ、再生塔に持ち込まれる炭化水素の量をより低減することができるので、安定した運転が可能となるので、結果として流動接触分解ガソリンの収率が向上する。 As the operating conditions of the reaction tower, the outlet temperature of the reaction tower is preferably 450 ° C. or higher, more preferably 470 ° C. or higher, further preferably 490 ° C. or higher, and the upper limit is preferably 550 ° C. or lower, more preferably 540 ° C. or higher. Below, it is more preferably 530 ° C. or lower. Under such reaction conditions, the progress of the cracking reaction can be further promoted, the non-evaporable hydrocarbons on the fluid catalytic cracking catalyst can be further reduced, and the amount of hydrocarbons brought into the regeneration tower can be further reduced. As a result, stable operation is possible, and as a result, the yield of liquid cracking gasoline is improved.
再生塔における運転温度は好ましくは６１５℃以上、より好ましくは６２０℃以上であり、上限として好ましくは６４５℃以下、より好ましくは６３５℃以下である。再生温度が６１５℃以上であると、コークを十分に燃焼できるため、触媒活性が向上する。一方、再生温度が６４５℃以下であると、コークの燃焼によるスチームの発生をより抑制し、触媒活性の劣化（水熱熱劣化）をより抑制できるため、触媒活性が向上する。また、触媒の循環量が低下することなく、分解率が向上するため、結果として流動接触分解ガソリンの収率が向上する。また、上記運転温度の範囲は、通常の再生塔の運転温度が６６０〜７２０℃程度であることを考慮すると、低い温度範囲で再生塔を運転しているといえる。本実施形態においては、流動接触分解触媒の投入量に対して原料油の供給量を調整することで、装置内流動接触分解触媒（平衡触媒）を所定のバナジウム相当金属量とするとともに、該触媒の残留炭素分を制御し、結果として流動接触分解ガソリンの収率の向上を図っているが、再生塔の運転温度を通常より低くできることは、該調整による副次的な効果ともいえる。また、原料油中の脱硫重油の含有量を上記範囲内とし、かつ脱硫重油以外の留分として上記例示したもの、中でも好ましくは重質軽油（ＨＧＯ）、減圧軽油（ＶＧＯ）、より好ましくは重質軽油（ＨＧＯ）が含有させることにより、相対的に重油留分の含有量が低減するので、再生塔の運転温度をより低下させやすくなる。 The operating temperature in the regeneration tower is preferably 615 ° C. or higher, more preferably 620 ° C. or higher, and the upper limit is preferably 645 ° C. or lower, more preferably 635 ° C. or lower. When the regeneration temperature is 615 ° C. or higher, the coke can be sufficiently burned, so that the catalytic activity is improved. On the other hand, when the regeneration temperature is 645 ° C. or lower, the generation of steam due to the combustion of cork can be further suppressed, and the deterioration of the catalytic activity (hydrothermal deterioration) can be further suppressed, so that the catalytic activity is improved. In addition, the cracking rate is improved without reducing the circulation amount of the catalyst, and as a result, the yield of liquid catalytic cracking gasoline is improved. Further, in the above operating temperature range, it can be said that the regenerated tower is operated in a low temperature range, considering that the operating temperature of the normal regenerated tower is about 660 to 720 ° C. In the present embodiment, by adjusting the supply amount of the raw material oil with respect to the input amount of the fluid cracking catalyst, the fluid cracking catalyst (equilibrium catalyst) in the apparatus is set to a predetermined vanadium-equivalent metal amount, and the catalyst is used. Although the residual carbon content of the above is controlled and the yield of cracked cracked gasoline is improved as a result, it can be said that the fact that the operating temperature of the regeneration tower can be made lower than usual is a secondary effect of the adjustment. Further, the content of the desulfurized heavy oil in the raw material oil is within the above range, and the fractions other than the desulfurized heavy oil are exemplified above, preferably heavy light oil (HGO), reduced pressure light oil (VGO), and more preferably heavy. By containing the quality light oil (HGO), the content of the heavy oil fraction is relatively reduced, so that the operating temperature of the regeneration tower can be more easily lowered.
以下に、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に何ら制限されるものではない。 Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.
（測定方法）
１．原料油中のバナジウム含有量及びニッケル含有量
石油学会規格ＪＰＩ−５Ｓ−５９−９９に準拠して測定した。測定したバナジウム含有量をＶ（質量ｐｐｍ）、ニッケル含有量をＮｉ（質量ｐｐｍ）とし、以下の式によりバナジウム相当金属量を算出した。
Ｖｅｑ＝Ｖ＋１／４×Ｎｉ
２．触媒の比表面積
ＢＥＴ窒素吸着法（ＡＳＴＭ Ｄ４３６５−９５）に準拠して測定し、算出した。
３．触媒の細孔容量
ＡＳＴＭ Ｄ４２２２−０３、Ｄ４６４１−９４に規定される窒素吸着、脱着等温線から算出した（Ｎ２吸着法）。
４．触媒上のバナジウム相当金属量
装置内流動接触分解触媒上のバナジウム相当金属量について、ＡＳＴＭ Ｄ７０８５−０４：Ｓｔａｎｄａｒｄ Ｇｕｉｄｅ ｆｏｒ Ｄｅｔｅｒｍｉｎａｔｉｏｎ ｏｆ Ｃｈｅｍｉｃａｌ Ｅｌｅｍｅｎｔｓ ｉｎ Ｆｌｕｉｄ Ｃａｔａｌｙｔｉｃ Ｃｒａｃｋｉｎｇ Ｃａｔａｌｙｓｔｓ ｂｙ Ｘ−ｒａｙ Ｆｌｕｏｒｅｓｃｅｎｃｅ Ｓｐｅｃｔｒｏｍｅｔｒｙ（ＸＲＦ）に基づき算出した。
５．触媒上の残留炭素分
装置内流動接触分解触媒上の残留炭素分について、炭素・硫黄分析装置（「ＥＭＩＡ−９２０Ｖ２（型番）」、株式会社堀場製作所製）を用いて測定した。
(Measuring method)
1. 1. Vanadium content and nickel content in raw material oil Measured according to the Petroleum Society standard JPI-5S-59-99. The measured vanadium content was V (mass ppm), the nickel content was Ni (mass ppm), and the vanadium-equivalent metal content was calculated by the following formula.
Veq = V + 1/4 x Ni
2. Specific surface area of catalyst Measured and calculated according to the BET nitrogen adsorption method (ASTM D4365-95).
3. 3. Pore capacity of catalyst Calculated from nitrogen adsorption and desorption isotherms specified in ASTM D4222-03 and D4641-94 (N 2 adsorption method).
4. Amount of metal equivalent to vanadium on the catalyst Regarding the amount of metal equivalent to vanadium on the fluidized contact decomposition catalyst in the device, ASTM D7085-04: Standard Guide for Determination of Chemical Elements in Fluoric Cracking Catalyst did.
5. Residual carbon content on the catalyst The residual carbon content on the fluidized cracking catalyst in the device was measured using a carbon / sulfur analyzer (“EMIA-920V2 (model number)”, manufactured by HORIBA, Ltd.).
（実施例１）
以下のようにして原料油の流動接触分解反応を行った。
下記留分を含み、第１表に示される性状を有する原料油を、下記の流動接触分解触媒を循環させる流動接触分解装置の反応塔に供給し、第１表に示される原料油の通油量、流動接触分解触媒の投入量、流動接触分解触媒上のバナジウム相当金属量及び残留炭素分となるようにしながら、分解反応を行った。
（原料油の性状）
脱硫重油 含有量：３０容量％
脱硫軽油 含有量：７０容量％
（流動接触分解触媒）
成分：超安定性Ｙ型ゼオライトを２５質量％、アルミナを５質量％、粘土鉱物を６０質量％、シリカ５質量％、その他不純物等含め５質量％を含有する触媒を用いた。
比表面積：２５０ｍ２／ｇ
細孔容量：０．２０ｃｍ３／ｇ
（流動接触分解装置の運転条件）
反応塔出口温度（ＲＯＴ）：５１８℃±３℃
再生塔の運転温度：６３０±３℃
触媒循環量：４８±１ｔｏｎ／ｍｉｎ
(Example 1)
The liquid catalytic cracking reaction of the raw material oil was carried out as follows.
The raw material oil containing the following distillate and having the properties shown in Table 1 is supplied to the reaction tower of the fluid catalytic cracking apparatus that circulates the following fluid catalytic cracking catalyst, and the raw material oil shown in Table 1 is passed. The cracking reaction was carried out while adjusting the amount, the amount of the fluid catalytic cracking catalyst to be charged, the amount of vanadium-equivalent metal on the fluid cracking catalyst and the residual carbon content.
(Characteristics of raw material oil)
Desulfurized heavy oil content: 30% by volume
Desulfurized gas oil content: 70% by volume
(Flowable cracking catalyst)
Ingredients: A catalyst containing 25% by mass of hyperstable Y-zeolite, 5% by mass of alumina, 60% by mass of clay mineral, 5% by mass of silica, and 5% by mass including other impurities was used.
Specific surface area: 250m 2 / g
Pore capacity: 0.20 cm 3 / g
(Operating conditions of the fluid catalytic cracker)
Reaction tower outlet temperature (ROT): 518 ° C ± 3 ° C
Operating temperature of the regeneration tower: 630 ± 3 ° C
Catalyst circulation amount: 48 ± 1 ton / min
（実施例２及び比較例１）
実施例１において、流動接触分解触媒の投入量に対する該原料油中のバナジウム相当金属量を第１表に記載の量とした以外は、実施例１と同様にして分解反応を行った。流動接触分解ガソリンの収率等を第１表に示す。
(Example 2 and Comparative Example 1)
In Example 1, the decomposition reaction was carried out in the same manner as in Example 1 except that the amount of vanadium-equivalent metal in the raw material oil was set to the amount shown in Table 1 with respect to the amount of the fluidized catalytic cracking catalyst input. Table 1 shows the yields of liquid cracked gasoline.
上記結果から、実施例では流動接触分解触媒の投入量に対する原料油中のバナジウム相当金属量を１．５０、１．２１質量％と０．４質量％以上４．０質量％以下の範囲内とし、装置内流動接触分解触媒（平衡触媒）の残留炭素分を０．０５質量％超０．５０質量％以下の範囲内とすることで、６１．８％、６１．５％という優れた流動接触分解ガソリンの収率が得られた。
また、従来法による比較例１では、流動接触分解触媒の投入量に対する原料油中のバナジウム相当金属量が０．２０質量％と０．４質量％以上４．０質量％以下の範囲外とすると、装置内流動接触分解触媒（平衡触媒）の残留炭素分が０．５８質量％と０．０５質量％超０．５０質量％以下の範囲外となり、流動接触分解ガソリンの収率は６０．０％に留まった。よって、本実施形態の流動接触分解ガソリンの製造方法によれば、従来法に比べて収率は１．５〜１．８％向上することが確認された。
From the above results, in the examples, the amount of vanadium-equivalent metal in the raw material oil was 1.50, 1.21% by mass, which was within the range of 0.4% by mass or more and 4.0% by mass or less with respect to the input amount of the fluid cracking catalyst. By setting the residual carbon content of the cracking catalyst (equilibrium catalyst) in the device within the range of more than 0.05% by mass and 0.50% by mass or less, excellent flow contact of 61.8% and 61.5% The yield of cracked gasoline was obtained.
Further, in Comparative Example 1 by the conventional method, it is assumed that the amount of vanadium-equivalent metal in the raw material oil is 0.20% by mass and 0.4% by mass or more and 4.0% by mass or less with respect to the input amount of the fluid cracking catalyst. , The residual carbon content of the fluid cracking catalyst (equilibrium catalyst) in the device is 0.58% by mass, which is outside the range of more than 0.05% by mass and 0.50% by mass or less, and the yield of cracked cracking gasoline is 60.0. Stayed at%. Therefore, according to the method for producing fluidly cracked gasoline of the present embodiment, it was confirmed that the yield was improved by 1.5 to 1.8% as compared with the conventional method.
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