JP2007077324A - Method for treating plastic cracked oil - Google Patents
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- JP2007077324A JP2007077324A JP2005268612A JP2005268612A JP2007077324A JP 2007077324 A JP2007077324 A JP 2007077324A JP 2005268612 A JP2005268612 A JP 2005268612A JP 2005268612 A JP2005268612 A JP 2005268612A JP 2007077324 A JP2007077324 A JP 2007077324A
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- 229920003023 plastic Polymers 0.000 title claims abstract description 68
- 239000004033 plastic Substances 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000003921 oil Substances 0.000 claims abstract description 100
- 239000003208 petroleum Substances 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000011575 calcium Substances 0.000 claims abstract description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 12
- 238000005504 petroleum refining Methods 0.000 claims abstract description 9
- 239000010936 titanium Substances 0.000 claims abstract description 9
- 239000002699 waste material Substances 0.000 claims abstract description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000004821 distillation Methods 0.000 claims description 16
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 4
- 238000004523 catalytic cracking Methods 0.000 claims description 3
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 3
- 239000003350 kerosene Substances 0.000 abstract description 16
- 239000007789 gas Substances 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 11
- 239000003502 gasoline Substances 0.000 abstract description 9
- 239000000295 fuel oil Substances 0.000 abstract description 8
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 238000004227 thermal cracking Methods 0.000 abstract description 2
- 239000011369 resultant mixture Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 238000004939 coking Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 5
- 238000000197 pyrolysis Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005443 coulometric titration Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Abstract
Description
本発明は、廃プラスチックの熱分解によって生成するプラスチック分解油を石油精製工程において石油留分とともに処理し、ガソリン基材原料や石油化学原料及び灯軽油となるナフサ留分や灯軽油留分並びに重油などを製造する方法に関する。 The present invention treats a plastic cracked oil produced by thermal decomposition of waste plastic together with a petroleum fraction in a petroleum refining process, and forms a naphtha fraction, a kerosene oil fraction, and a heavy oil to become a gasoline base material, a petrochemical raw material, and a kerosene. The present invention relates to a method for manufacturing such as.
一般に原油から製造されるガソリン基材原料や石油化学原料となるナフサ留分や灯油・軽油留分は需要が旺盛である。この原料としては、直留ナフサ、減圧ナフサ、熱分解ナフサ、直留灯油、減圧灯油、熱分解灯油、直留軽油、減圧軽油、熱分解軽油など原油からえられる石油留分が用いられている。 In general, there is a strong demand for naphtha fractions, kerosene and light oil fractions, which are gasoline base materials and petrochemical materials produced from crude oil. As this raw material, petroleum fractions obtained from crude oil such as straight-run naphtha, vacuum naphtha, pyrolysis naphtha, straight-run kerosene, vacuum kerosene, pyrolysis kerosene, straight-run gas oil, vacuum gas oil, and pyrolysis gas oil are used. .
プラスチック分解油は、廃棄物などから分離されたプラスチックの分解によって生成する油分である。原料となるプラスチックは、特に限定されるものではないが、ポリエチレン、ポリプロピレンなどのポリオレフィン、ポリスチレンなどのスチレン系樹脂、ポリアミド樹脂、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリカーボネートなどが挙げられる。通常は、廃棄されたプラスチックを原料とする。このようなプラスチックの熱分解反応は公知である（特許文献１、２参照）。 Plastic cracked oil is an oil produced by cracking plastic separated from waste or the like. The raw material plastic is not particularly limited, and examples thereof include polyolefins such as polyethylene and polypropylene, styrene resins such as polystyrene, polyamide resins, polyvinyl chloride, polyvinylidene chloride, and polycarbonate. Usually, discarded plastic is used as a raw material. Such a thermal decomposition reaction of plastic is known (see Patent Documents 1 and 2).
このプラスチック分解油は一般的にボイラー燃料などに用いられており、不純物が多いことからガソリン基材や灯軽油、石油化学原料として利用されていない。廃プラスチック中、ポリアミド樹脂、ポリウレタン類、ＡＢＳ樹脂及びＮＢＲには窒素が含有され、ポリ塩化ビニル（ＰＶＣ）、ポリ塩化ビニリデン（ＰＶＤＣ）、塩化ポリエチレンには塩素が含有される。このため、プラスチック分解油中には塩素分、窒素分などの不純物が比較的多く残存しており、これを除去するために、プラスチック分解油を水素化精製することが提案されている（特許文献３〜５参照）。 This plastic cracked oil is generally used for boiler fuel and the like, and since it has many impurities, it is not used as a gasoline base material, kerosene oil, or petrochemical raw material. Among waste plastics, polyamide resins, polyurethanes, ABS resins, and NBR contain nitrogen, and polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), and polyethylene chloride contain chlorine. For this reason, a relatively large amount of impurities such as chlorine and nitrogen remain in the plastic cracked oil, and it has been proposed to hydrotreat the plastic cracked oil in order to remove this (patent document). 3-5).
しかし、プラスチック分解油をそのままでは、実質的には水素化精製することができない。プラスチック分解油には不純物として金属分が多く含まれていることがある。この金属分は、水素化精製時の触媒を被毒する。このため、水素化精製にともない触媒の活性が急速に低下してしまい、長時間安定に運転することができない。または、水素化精製のためにプラスチック分解油を加熱して触媒床に導入すると、触媒表面及び導入部にコーキングしてしまい、通油が困難になることがある。
本発明はこのようなプラスチック分解油の水素化精製におけるコーキングなどの問題点を解決し、通常の石油精製工程における処理によってプラスチック分解油をガソリン基材原料や石油化学原料及び灯軽油となるナフサ留分及び灯軽油留分、重油基材として利用することを目的とするものである。 The present invention solves such problems as coking in the hydrorefining of plastic cracked oil, and the naphtha distillate that turns plastic cracked oil into gasoline base material, petrochemical feedstock and kerosene oil by processing in a normal oil refining process. It is intended to be used as a fraction, kerosene fraction, and heavy oil base material.
本発明によるプラスチック分解油の処理方法は、廃プラスチックの熱分解によって生成するプラスチック分解油と石油留分を混合し、石油精製工程おいて処理するプラスチック分解油の処理方法であって、前記プラスチック分解油と石油留分を混合した混合原料油は、カルシウムの含有量が金属換算で２質量ｐｐｍ以下であることを特徴とし、さらに、チタンおよびシリコンの含有量がそれぞれ金属換算で２質量ｐｐｍ以下であることが好ましい。 A method for treating plastic cracked oil according to the present invention is a method for treating plastic cracked oil in which a plastic fraction oil generated by thermal cracking of waste plastic and a petroleum fraction are mixed and treated in an oil refining process, wherein The mixed raw material oil mixed with oil and petroleum fraction is characterized in that the calcium content is 2 mass ppm or less in terms of metal, and the titanium and silicon contents are each 2 mass ppm or less in terms of metal. Preferably there is.
前記プラスチック分解油は、カルシウム含有量が金属換算で５０質量ｐｐｍ以下であることが好ましく、さらには、チタンおよびシリコンの含有量が金属換算でそれぞれ５０質量ｐｐｍ以下であることが好ましい。 The plastic cracked oil preferably has a calcium content of 50 mass ppm or less in terms of metal, and more preferably has a titanium and silicon content of 50 mass ppm or less in terms of metal, respectively.
前記石油留分の９０％留出温度と、前記プラスチック分解油の９０％留出温度との差が２００℃以下であることが好ましい。前記石油留分の９０％留出温度が、３００℃を超え、６００℃以下であることが好ましい。 The difference between the 90% distillation temperature of the petroleum fraction and the 90% distillation temperature of the plastic cracked oil is preferably 200 ° C or less. The 90% distillation temperature of the petroleum fraction is preferably more than 300 ° C and not more than 600 ° C.
前記石油精製工程は、水素化精製、水素化分解および接触分解の少なくとも一つの工程を含むことが好ましい。 The petroleum refining step preferably includes at least one step of hydrorefining, hydrocracking and catalytic cracking.
本発明は、プラスチック分解油や混合原料油中のカルシウムなどの金属の含有量を所定の値以下にコントロールして供給することで、水素化精製などの石油精製工程においてコーキング、スラッジなどの発生を抑制することができ、プラスチック分解油と石油留分とを同時に容易に処理することができる。したがって、プラスチック分解油から塩素分、窒素分などの不純物含有量の少ない精製油を得ることができ、ガソリン基材原料や石油化学原料、灯軽油および重油として利用することができる。 The present invention controls the generation of coking, sludge, etc. in petroleum refining processes such as hydrorefining by controlling the content of metals such as calcium in plastic cracked oil and mixed raw material oil to a predetermined value or less. It is possible to suppress the plastic cracked oil and the petroleum fraction easily at the same time. Accordingly, a refined oil having a small content of impurities such as chlorine and nitrogen can be obtained from the plastic cracked oil, and can be used as a gasoline base material, petrochemical raw material, kerosene oil and heavy oil.
〔プラスチック分解油〕
プラスチック分解油は、廃プラスチックの熱分解によって得られたものであり、カルシウム（Ｃａ）の含有量が金属換算で５０質量ｐｐｍ以下にものが好ましく、特には１０質量ｐｐｍ以下、さらには２質量ｐｐｍ以下が好ましい。また、チタン（Ｔｉ）及びシリコン（Ｓｉ）の含有量が金属換算でそれぞれ５０質量ｐｐｍ以下、特には１０質量ｐｐｍ以下、さらには２質量ｐｐｍ以下であることが好ましい。このようなプラスチック分解油は、金属含有量の少ないプラスチック分解油を選別することで得ることができる。また、廃プラスチック熱分解の原料となる廃プラスチックを選別することで金属含有量を下げることができる。
[Plastic decomposition oil]
The plastic decomposition oil is obtained by thermal decomposition of waste plastic, and the calcium (Ca) content is preferably 50 mass ppm or less in terms of metal, particularly 10 mass ppm or less, more preferably 2 mass ppm. The following is preferred. Moreover, it is preferable that content of titanium (Ti) and silicon (Si) is 50 mass ppm or less, especially 10 mass ppm or less, more preferably 2 mass ppm or less, respectively in terms of metal. Such plastic cracked oil can be obtained by selecting a plastic cracked oil having a low metal content. In addition, the metal content can be reduced by selecting waste plastic as a raw material for waste plastic pyrolysis.
プラスチック分解油の性状としては、硫黄分が２００００ｐｐｍ以下、特には３００ｐｐｍ以下、窒素分が２０００ｐｐｍ以下、特には１５００ｐｐｍ以下、塩素分が１〜１０００ｐｐｍ、特には１０〜１００ｐｐｍ、臭素価が１．５ｇＢｒ2／１００ｇ以上、特には１０〜３００ｇＢｒ2／１００ｇ、ジエン価が０．３ｇ／１００ｇ以上、特には１〜５ｇ／１００ｇ、その他金属分（マグネシウム（Ｍｇ）、鉄（Ｆｅ）、アルミニウム（Ａｌ）、銅（Ｃｕ）、ニッケル（Ｎｉ）、バナジウム（Ｖ））が５０ｐｐｍ以下、特には１０ｐｐｍ以下であることが好ましい。なお、不純物などがこの範囲を外れる場合には、吸着、ろ過、遠心分離などの除去処理により予めプラスチック分解油を処理して不純物を除去することもできる。 As the properties of the plastic cracked oil, the sulfur content is 20000 ppm or less, particularly 300 ppm or less, the nitrogen content is 2000 ppm or less, particularly 1500 ppm or less, the chlorine content is 1-1000 ppm, particularly 10-100 ppm, and the bromine number is 1.5 gBr 2. / 100g or more, particularly 10～300GBr 2 / 100g, diene value 0.3 g / 100g or more, particularly 1 to 5 g / 100g, other metal component (magnesium (Mg), iron (Fe), aluminum (Al), Copper (Cu), nickel (Ni), vanadium (V)) is preferably 50 ppm or less, particularly preferably 10 ppm or less. In addition, when an impurity etc. remove | deviates from this range, a plastic decomposition oil can be previously processed by removal processes, such as adsorption | suction, filtration, and centrifugation, and an impurity can also be removed.
プラスチック分解油の蒸留性状としては、
９０％留出温度が１００〜６００℃、特には３００℃を超える、さらには４００℃を超えることが好ましい。
初留点は３００℃以下、特には１００℃以下が好ましい。
５０％留出温度が１００〜５００℃、特には１５０〜３５０℃が好ましい。
As the distillation properties of plastic cracked oil,
It is preferable that the 90% distillation temperature is 100 to 600 ° C, particularly 300 ° C or more, more preferably 400 ° C.
The initial boiling point is preferably 300 ° C. or lower, particularly preferably 100 ° C. or lower.
The 50% distillation temperature is preferably 100 to 500 ° C, particularly 150 to 350 ° C.
〔石油留分〕
石油留分の蒸留性状について、９０％留出温度は、３００〜６００℃、特には４００〜６００℃が好ましく、プラスチック分解油の９０％留出温度との差が、２００℃以下、特には１００℃以下であることが好ましい。石油留分の芳香族分は、１０〜５０％、特には２０〜４０％が好ましい。石油留分の９０％留出温度がこの範囲であれば、石油留分中に多くの芳香族分を有し、溶解性が高いため、コーキングを抑制しながら処理できるため、好ましい。
[Oil fraction]
Regarding the distillation characteristics of petroleum fractions, the 90% distillation temperature is preferably 300 to 600 ° C., particularly preferably 400 to 600 ° C., and the difference from the 90% distillation temperature of the plastic cracked oil is 200 ° C. or less, particularly 100 It is preferable that it is below ℃. The aromatic content of the petroleum fraction is preferably 10 to 50%, particularly preferably 20 to 40%. If the 90% distillation temperature of the petroleum fraction is within this range, it is preferable because the petroleum fraction has a large amount of aromatic content and has high solubility, and can be treated while suppressing coking.
石油留分は、原油を原料として得られた炭化水素からなる留分であれば特に限定はなく、例えば、直留ナフサ、減圧ナフサ、熱分解ナフサ、直留灯油、減圧灯油、熱分解灯油、直留軽油、減圧軽油、熱分解軽油などやこれらの任意な混合物が挙げられる。 The petroleum fraction is not particularly limited as long as it is a fraction made of hydrocarbons obtained from crude oil as a raw material. Examples include straight-run gas oil, vacuum gas oil, pyrolysis gas oil, and any mixture thereof.
石油留分は、硫黄分が０．０５〜１０％、特には０．１〜５％、窒素分が１０〜５０００ｐｐｍ、特には２０〜２０００ｐｐｍであることが好ましい。金属（カルシウム、チタン、シリコン、マグネシウム、鉄、アルミニウム、銅、ニッケル、バナジウム）の含有量がそれぞれ５００ｐｐｍ以下、特には５０ｐｐｍ以下であることが好ましい。 The petroleum fraction preferably has a sulfur content of 0.05 to 10%, particularly 0.1 to 5%, and a nitrogen content of 10 to 5000 ppm, particularly 20 to 2000 ppm. The content of metals (calcium, titanium, silicon, magnesium, iron, aluminum, copper, nickel, vanadium) is preferably 500 ppm or less, particularly 50 ppm or less.
〔混合原料油〕
プラスチック分解油と石油留分を混合した混合原料油は、カルシウムの含有量が金属換算で２質量ｐｐｍ以下、好ましくは１質量ｐｐｍ以下である。チタン及びシリコンの含有量が金属換算でそれぞれ２質量ｐｐｍ以下、好ましくは１質量ｐｐｍ以下であることが望ましい。
[Mixed feed oil]
The mixed raw material oil obtained by mixing the plastic cracked oil and the petroleum fraction has a calcium content of 2 mass ppm or less, preferably 1 mass ppm or less in terms of metal. The contents of titanium and silicon are each 2 ppm by mass or less, preferably 1 ppm by mass or less in terms of metal.
プラスチック分解油の混合割合は、処理対象全体に対して５０容量％以下、特には２５容量％以下、さらには２０容量％以下が好ましい。この範囲を超える場合にはコーキング及び／又は腐食が予想され、処理が困難になることが予想される。 The mixing ratio of the plastic cracked oil is preferably 50% by volume or less, particularly 25% by volume or less, and more preferably 20% by volume or less with respect to the entire processing target. If this range is exceeded, coking and / or corrosion is expected and processing is expected to be difficult.
〔石油精製工程〕
プラスチック分解油と石油留分を混合した混合原料油を処理する石油精製工程は、水素化精製、水素化分解および接触分解の少なくとも一つの工程を含むものであり、特に、水素化精製の工程が好ましい。これにより、石油留分の硫黄分、窒素分、金属分などが低減されるとともに、プラスチック分解油の窒素分、塩素分、金属分などが低減される。硫黄分が０．５〜５％、特には１％以上の石油留分をプラスチック分解油と混合して、水素化精製により硫黄分が０．２％以下、特には０．１％以下とするような精製工程が好ましい。
[Oil refinery process]
The petroleum refining process for treating the mixed feedstock obtained by mixing plastic cracked oil and petroleum fraction includes at least one process of hydrorefining, hydrocracking and catalytic cracking. preferable. Thereby, the sulfur content, nitrogen content, metal content, etc. of the petroleum fraction are reduced, and the nitrogen content, chlorine content, metal content, etc. of the plastic cracked oil are reduced. Petroleum fraction with sulfur content of 0.5-5%, especially 1% or more is mixed with plastic cracked oil, and sulfur content is 0.2% or less, especially 0.1% or less by hydrorefining. Such a purification step is preferred.
水素化精製は処理油を水素の存在下で水素化精製触媒と接触させるものである。水素化精製触媒は、アルミナなどの無機多孔質担体にモリブデン、ニッケル、コバルト、リンのうち少なくとも一種を、特にモリブデンとニッケルまたはコバルトの少なくとも一方を担持した触媒が好ましく用いられる。好ましい反応条件は反応温度：２５０〜４５０℃、反応圧力：１〜２５ＭＰａ、ＬＨＳＶ（液空間速度）：０．１〜３０ｈ-1、Ｈ2／Ｏｉｌ（水素／油比）：２０〜２０００Ｌ／Ｌである。 Hydrorefining involves contacting the treated oil with a hydrorefining catalyst in the presence of hydrogen. As the hydrorefining catalyst, a catalyst in which at least one of molybdenum, nickel, cobalt, and phosphorus is supported on an inorganic porous carrier such as alumina, and particularly at least one of molybdenum and nickel or cobalt is preferably used. Preferred reaction conditions are: reaction temperature: 250 to 450 ° C., reaction pressure: 1 to 25 MPa, LHSV (liquid space velocity): 0.1 to 30 h −1 , H 2 / Oil (hydrogen / oil ratio): 20 to 2000 L / L It is.
水素化精製の後にナフサ留分、灯油留分、軽油留分、重質軽油留分などの留分に分けられ、そのまま、または、他の石油精製工程を経て、石化用ナフサ、ガソリン、灯油、軽油、重油などの製品または製品を構成する基材となる。特に、石化用ナフサ、ガソリン基材としては、硫黄分１０ｐｐｍ以下、特には２ｐｐｍ以下、窒素分１０ｐｐｍ以下、特には２ｐｐｍ以下、塩素分１０ｐｐｍ以下、特には１ｐｐｍ以下、全酸価０．０１ｍｇＫＯＨ／ｇ以下、ジエン価０．２ｇ／１００ｇ以下、特には０．１ｇ／１００ｇ以下とすることができる。 After hydrorefining, it is divided into fractions such as naphtha fraction, kerosene fraction, light oil fraction, heavy gas oil fraction, etc., or through other petroleum refining processes, naphtha for petrochemical, gasoline, kerosene, It becomes a base material constituting a product or product such as light oil and heavy oil. In particular, as petrochemical naphtha and gasoline base material, the sulfur content is 10 ppm or less, particularly 2 ppm or less, the nitrogen content is 10 ppm or less, particularly 2 ppm or less, the chlorine content is 10 ppm or less, particularly 1 ppm or less, and the total acid value is 0.01 mgKOH / g. Hereinafter, the diene value may be 0.2 g / 100 g or less, particularly 0.1 g / 100 g or less.
以下、実施例により本発明を説明するが、本実施例により本発明が限定的に解釈されるものではない。
なお、本実施例では密度はＪＩＳ Ｋ ２２４９に、硫黄分はＪＩＳ Ｋ ２５４１（紫外蛍光法）に、窒素分はＪＩＳ Ｋ ２６０９（化学発光法）に、塩素分は電量滴定法、臭素価はＪＩＳ Ｋ ２６０５に、ジエン価はＵＯＰ ３２６−６５に、蒸留性状はＪＩＳ Ｋ ２２５４、芳香族分はＦＩＡ、ＪＰＩ法、金属分はＩＣＰ発光分析法によって測定した。検出下限は、１質量ｐｐｍである。
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not interpreted limitedly by this Example.
In this example, the density is JIS K 2249, the sulfur content is JIS K 2541 (ultraviolet fluorescence method), the nitrogen content is JIS K 2609 (chemiluminescence method), the chlorine content is coulometric titration, and the bromine value is JIS. The diene value was measured by K 2605, the diene value by UOP 326-65, the distillation property by JIS K 2254, the aromatic content by FIA, JPI method, and the metal content by ICP emission analysis. The lower limit of detection is 1 ppm by mass.
実施例で用いたプラスチック分解油および石油留分の性状を表１にまとめる。プラスチック分解油は、容器包装プラスチック油化事業者協議会より入手したものの内、カルシウム含有量の少ないプラスチック分解油を選別したものである。石油留分は中東系原油を常圧蒸留して得られた重質軽油留分と、残油を減圧蒸留して得られた減圧軽油留分との混合油である。 The properties of the plastic cracked oil and petroleum fraction used in the examples are summarized in Table 1. The plastic cracked oil is obtained by selecting the plastic cracked oil with a low calcium content from those obtained from the Containers and Packaging Plastic Oil Company Association. The petroleum fraction is a mixed oil of a heavy gas oil fraction obtained by atmospheric distillation of Middle Eastern crude oil and a vacuum gas oil fraction obtained by distillation of the residual oil under reduced pressure.
表１の石油留分とプラスチック分解油を表２に示す割合で配合して混合原料油を用意した。この混合原料油を次の条件で水素化精製した。なお、この石油留分の芳香族分は３５．７質量％であった。 A mixed raw material oil was prepared by blending the petroleum fraction of Table 1 and the plastic cracked oil in the proportions shown in Table 2. This mixed feedstock was hydrorefined under the following conditions. The aromatic fraction of this petroleum fraction was 35.7% by mass.
上下方向長さ１１６０ｍｍ、内径１９ｍｍの固定床流通式反応器中に、上から順に、３φのアルミナボール約１００ｍｌと、６０ｍｌ（４９．２ｇ）の水素化精製触媒（ＡＲＴ社製 ＨＯＰ４７３）と、３φアルミナボール約２５ｍｌを充填し、混合原料油と水素を上端から導入した。反応条件は、温度：３５０℃、圧力８．０ＭＰａ、ＬＨＳＶ：２ｈ-1、Ｈ2／Ｏｉｌ：２３０Ｌ／Ｌの条件下にて水素化精製を行った。用いたＡＲＴ社製ＨＯＰ４７３は、アルミナを担体として金属としてモリブデンを１１ｗｔ％、ニッケルを３ｗｔ％、リン２ｗｔ％含有しているものである。 In a fixed-bed flow reactor having a vertical length of 1160 mm and an inner diameter of 19 mm, about 100 ml of 3φ alumina balls, 60 ml (49.2 g) of hydrorefining catalyst (ART HOP473), 3φ About 25 ml of alumina balls were filled, and mixed raw material oil and hydrogen were introduced from the upper end. The reaction conditions were hydrorefining under conditions of temperature: 350 ° C., pressure 8.0 MPa, LHSV: 2 h −1 , H 2 / Oil: 230 L / L. The used HOP473 manufactured by ART contains 11 wt% molybdenum, 3 wt% nickel, and 2 wt% phosphorus using alumina as a metal as a carrier.
その結果、実験終了（運転時間：７２０時間）まで差圧が上がることなく運転可能であり、また、触媒の水素化性能に影響は与えなかった。反応器内部は、コーキングは発生せず、油が流れる状態であった。カルシウムなどの金属含有量の多いプラスチック分解油を用いた場合には、触媒の被毒及び／又は反応器内部にコーキングの発生が予想され、長期の水素化精製処理が困難となることが予想される。得られた精製油全体の性状及び、その精製油全体を分留した各留分の性状を表３に示す。 As a result, the operation was possible without increasing the differential pressure until the end of the experiment (operation time: 720 hours), and the hydrogenation performance of the catalyst was not affected. Inside the reactor, coking did not occur and oil was flowing. When plastic cracked oil with a high metal content such as calcium is used, catalyst poisoning and / or coking inside the reactor is expected, and long-term hydrorefining treatment is expected to be difficult. The Table 3 shows the properties of the entire refined oil obtained and the properties of each fraction obtained by fractionating the entire refined oil.
本発明は、プラスチック分解油と石油留分を混合した混合原料油について、カルシウムなどの含有量を所定値以下となるように混合し、水素化精製などの石油精製処理を行うものであるので、コーキングなどにより、処理が困難になることがなく、塩素、窒素などの不純物を低減することができるので、精製したナフサ留分、灯油・軽油留分及び重油基材はガソリン基材原料や石油化学原料、灯油、軽油及び重油として利用することができる。
Since the present invention is a mixed feedstock obtained by mixing plastic cracked oil and petroleum fraction, the content of calcium and the like is mixed so as to be a predetermined value or less, and petroleum refining treatment such as hydrorefining is performed. Because processing such as coking does not become difficult and impurities such as chlorine and nitrogen can be reduced, refined naphtha fractions, kerosene / light oil fractions and heavy oil bases are used as gasoline base materials and petrochemicals. It can be used as a raw material, kerosene, light oil and heavy oil.
Claims (7)
The method for treating plastic cracked oil according to any one of claims 1 to 6, wherein the petroleum refining step includes at least one step of hydrorefining, hydrocracking, and catalytic cracking.
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| WO2013070801A1 (en) * | 2011-11-10 | 2013-05-16 | Natural State Research, Inc. | Methods and systems for converting plastic to fuel |
| US8927797B2 (en) | 2008-05-30 | 2015-01-06 | Natural State Research, Inc. | Method for converting waste plastic to lower-molecular weight hydrocarbons, particularly hydrocarbon fuel materials, and the hydrocarbon material produced thereby |
| GB2580539A (en) * | 2018-12-28 | 2020-07-22 | Neste Oyj | Method for co-processing |
| WO2021204821A1 (en) | 2020-04-07 | 2021-10-14 | Total Research & Technology Feluy | Purification of waste plastic based oil via first a trap and second via an hydrotreatment |
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| JP2005105027A (en) * | 2003-09-29 | 2005-04-21 | Japan Energy Corp | Manufacturing method of naphtha fraction |
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| JPS63159493A (en) * | 1986-08-28 | 1988-07-02 | シエブロン リサ−チ カンパニ− | Removal of metal from hydrocarbon feed raw material using sequestering agent |
| JPH10310778A (en) * | 1997-05-12 | 1998-11-24 | Mitsubishi Oil Co Ltd | Purification of oil made from waste plastic and purified fraction |
| JP2005105027A (en) * | 2003-09-29 | 2005-04-21 | Japan Energy Corp | Manufacturing method of naphtha fraction |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US8927797B2 (en) | 2008-05-30 | 2015-01-06 | Natural State Research, Inc. | Method for converting waste plastic to lower-molecular weight hydrocarbons, particularly hydrocarbon fuel materials, and the hydrocarbon material produced thereby |
| US9404046B2 (en) | 2008-05-30 | 2016-08-02 | Natural State Research, Inc. | Method for converting waste plastic to lower-molecular weight hydrocarbons, particularly hydrocarbon fuel materials, and the hydrocarbon material produced thereby |
| WO2013070801A1 (en) * | 2011-11-10 | 2013-05-16 | Natural State Research, Inc. | Methods and systems for converting plastic to fuel |
| GB2580539A (en) * | 2018-12-28 | 2020-07-22 | Neste Oyj | Method for co-processing |
| GB2580539B (en) * | 2018-12-28 | 2021-04-14 | Neste Oyj | Method for co-processing |
| WO2021204821A1 (en) | 2020-04-07 | 2021-10-14 | Total Research & Technology Feluy | Purification of waste plastic based oil via first a trap and second via an hydrotreatment |
| WO2021204820A1 (en) | 2020-04-07 | 2021-10-14 | Total Research & Technology Feluy | Purification of waste plastic based oil with a high temperature hydroprocessing |
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