JPH0438084B2 - - Google Patents
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- Publication number
- JPH0438084B2 JPH0438084B2 JP59021849A JP2184984A JPH0438084B2 JP H0438084 B2 JPH0438084 B2 JP H0438084B2 JP 59021849 A JP59021849 A JP 59021849A JP 2184984 A JP2184984 A JP 2184984A JP H0438084 B2 JPH0438084 B2 JP H0438084B2
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- Prior art keywords
- oil
- pyrolysis
- reaction product
- fraction
- boiling point
- Prior art date
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- 239000003921 oil Substances 0.000 claims description 64
- 238000000034 method Methods 0.000 claims description 41
- 238000000197 pyrolysis Methods 0.000 claims description 32
- 239000007795 chemical reaction product Substances 0.000 claims description 30
- 238000004939 coking Methods 0.000 claims description 16
- -1 aliphatic olefins Chemical class 0.000 claims description 15
- 238000009835 boiling Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 11
- 238000005984 hydrogenation reaction Methods 0.000 claims description 10
- 239000003377 acid catalyst Substances 0.000 claims description 9
- 239000010735 electrical insulating oil Substances 0.000 claims description 8
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical group 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 description 14
- 239000000571 coke Substances 0.000 description 11
- 238000000354 decomposition reaction Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 238000005979 thermal decomposition reaction Methods 0.000 description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000004227 thermal cracking Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 239000011344 liquid material Substances 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000005504 petroleum refining Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910016569 AlF 3 Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Landscapes
- Lubricants (AREA)
- Organic Insulating Materials (AREA)
Description
本発明は石油系重質残油を原料とする熱分解プ
ロセスからの熱分解油留分を処理することからな
る電気絶縁油の製造法に関する。
近年、石油資源の枯渇から、より重質な原油を
使用するようになり、このため、副生する蒸留残
渣油などの重質残油の量も増大する傾向にある。
しかるに、この重質残油は、高粘度であり、硫黄
分や金属分が多いなどの理由で工業的な利用価値
が少ない。
一方、このような重質残油の唯一とも言える利
用形態がコーキングに代表される熱分解プロセス
の原料として利用することである。この重質残油
のコーキングプロセスからは、コークス、ガスな
どとともに液状物すなわち熱分解油も得られる
が、通常コーキングにおける熱分解油の収率はか
なり高く、多量に熱分解油留分が得られることに
なる。
しかるに、従来よりこの多量に生成する熱分解
油の利用方法としては、この油が脂肪族炭化水素
が比較的多く、十分なオクタン価を有さないこと
もあり流動接解分解などの処理を更におこなわな
い限りはこのままでは自動用ガソリンには使用す
ることができず、ボイラー用などの単なる燃料と
して利用するのが限度であつた。したがつて、こ
の多量の熱分解油の利用は工業上の大きな問題と
なりつつある。
本発明の目的とするところは、上述の事情に鑑
み、たとえばコーキングプロセスにおいて、ボイ
ラー用燃料程度しか利用価値のない副産物として
多量に得られる熱分解油留分を処理して優れた電
気絶縁油を得ることにある。かくすることによ
り、当該熱分解油留分の有効利用が達成できる。
すなわち、本発明によれば石油系重質残油を
400℃以上で、700℃を越えない温度で熱分解して
得られる熱分解油留分を液相で酸触媒処理するこ
とにより、低粘度で低流動点の電気絶縁油が得ら
れる。
次に本発明を更に説明する。
本発明の石油系重質残油とは、石油精製業の通
常の意味における常圧蒸留残渣油、減圧蒸留残渣
油、熱分解もしくは接触分解残渣油、及び各種の
石油精製残留物、例えば、フルフラール、プロパ
ン、ペンタンなどによる抽出残油、リホーマー残
油など、及びこれらの混合物等をいう。
本発明の熱分解プロセスの分解温度は400℃以
上であつて、600℃を越えないことが必要である。
400℃より低い分解温度では熱分解がおこらず、
また600℃以上となると、分解時間の多少にかか
わらず、得られる熱分解油中に、それ自身反応性
の高い芳香族炭化水素が過剰になり、酸触媒処理
では樹脂分などの高重合体ができやすいととも
に、沸点が120〜290℃の範囲にあるような脂肪族
オレフイン量が過少となるので好ましくない。分
解温度は好ましくは、400〜550℃である。分解時
間は、当該熱分解プロセスの主たる目的、たとえ
ばコークス製造、原料重質油の粘度低下などによ
り適宜変更でき、例えば、10sec〜50hrなる範囲
で採用できる。分解の際には水蒸気、その他の非
反応性ガス状媒体を存在させることもできる。分
解圧力は通常は比較的低く、減圧ないし50Kg/cm2
程度である。
このような重質残油の熱分解プロセスの代表的
なものとしては、Hydrocarbon Processing,
Vol.61,No.9,September1982,pp.160〜163に
記載されているように、ビスブレーキング法やコ
ーキング法などがある。
すなわち、ビスブレーキング法は、加熱炉チユ
ーブ内でコークスの生成を抑制しつつ比較的温和
な条件で、主として原料の粘度低下を目的として
熱分解するプロセスであり、コイル型とソーカー
型がある。通常、分解炉を出た分解油は、分解や
コークス抑制のため急冷される。これには
Lummus法やShell法などがある。
また、コーキング法は、コークスを併産するプ
ロセスであるが、一旦、加熱炉内で比較的短時
間、残油を加熱した後、コークスドラムに送り、
ここで比較的長時間をかけて塊状コークスを生成
させるデイレードコーキング(UOP法、Foster
Wheeler法、M.W.Kellogg法、Lummus法及び
CONOCO法など)、高温の流動コークス上で残
油を残分解するフルーイドコーキング法
(Exxon法など)、フルーイドコーキング法に生
成コークスのガス化プロセスを結合させたフレキ
シコーキング法(Exxon法)及び、熱分解する
とともに常圧などの比較的低圧でスチームストリ
ツピングしてピツチを製造するユリカ
(EUREKA)プロセスなどがある。
これらの熱分解プロセスの中でも、残油中の硫
黄分や金属分が生成コークス中に濃縮される結
果、分解油中には比較的これら不純分が少なく、
したがつて、酸触媒処理後も精製が比較容器であ
る、また高沸点の脂肪族オレフインが比較的多量
に含まれているなどのためコーキング法が好まし
い。さらに、この中でも、デイレードコーキング
(delayed coking)は、電極用黒鉛などの炭素源
として有用な塊状コークスが得られるなどのため
大規模に稼動しており、そのため副生する分解油
も特に多量であるので、本発明によりその有効利
用を図ればその利益は多大であるので有利なコー
キング法である。
上記の熱分解プロセスから得られる熱分解油の
組成は熱分解プロセスのタイプ、熱分解条件、原
料の重質油の種類などによつて変動するが、通常
は、芳香族オレフインを殆んど含まず、主として
ノルマルパラフイン、イソパラフインなどのパラ
フインのほかに、反応性に富むノルマルオレフイ
ン、イソオレフインなどの脂肪族オレフインを含
み、さらに、アルキルベンゼンなどのようなアル
キル置換の単環、アルキルインダン、アルキルテ
トラリンなどのようなアルキル置換の複合環、お
よびアルキルナフタリンなどのようなアルキル置
換の縮合環などを有する芳香族炭化水素を含むも
のである。
上記の各種の熱分解プロセスから得られる熱分
解油のうち、本発明においては、沸点が120〜290
℃、より好ましくは150〜260℃の範囲にある炭化
水素を主成分とする熱分解油留分を処理の対象と
する。沸点範囲が上記をはずれる炭化水素を主成
分とする留分では、反応生成物が収率が劣るので
好ましくない。また、本発明の処理すべき熱分解
油留分は、芳香族炭化水素および脂肪族オレフイ
ンを含むことが必要である。芳香族炭化水素を含
まない留分では得られた反応生成物の流動点が高
くなるので好ましくない。脂肪族オレフインは該
留分中に10重量%以上含まれることが必要であつ
て、脂肪族オレフインがこれより少ない留分では
経済的な収率で反応生成物を回収することができ
ないので好ましくない。
通常の対象とする熱分解油留分の代表的組成は
パラフイン30〜70重量%、脂肪族オレフイン10〜
40重量%、芳香族炭化水素5〜20重量%である。
しかしながら、上述した対象留分の条件を満足す
る限り、熱分解油を適宜、分留したり、また未反
応油などで稀釈することは差しつかえない。
処理に用いる酸触媒は、固体酸触媒、鉱酸、いわ
ゆるフリーデル・クラフツ触媒、有機酸などが好
ましく用いられる。例えば具体的には、酸性白
土、活性白土などを代表する酸性粘土鉱物、無定
形もしくは結晶性のシリカ−アルミナ、AlF3・
Al2O3、強酸型のイオン交換樹脂などの固体酸触
媒、HF,AlCl3,BF3.CnCl4などのフリーデ
ル・クラフツ触媒、硫酸、パラトルエンスルホン
酸、トリフルオロメタンスルホン酸などの無機も
しくは有機酸である。
処理の反応形式は、バツチ式、セミバツチ式あ
るいは流通式のいずれでもよいが、固体酸を用い
る場合は流通式を用いるのが好ましい。
上記した酸触媒を当該留分に対して、バツチ式
では0.2〜20重量%、好ましくは1〜10重量%添
加し、また流通式ではLHSV0.1〜20、好ましく
は0.5〜10の条件で処理する。反応温度は30〜330
℃、好ましくは50〜250℃である。処理時間は反
応条件、すなわち、触媒量、反応温度、原料組成
などによつて異なるが、反応完結に十分なる時間
が必要であり、通常2〜24時間の範囲で選ぶこと
ができる。反応圧力は反応相を液相に保つに必要
な圧力であれば良い。
本発明においては、上記酸触媒処理を、該熱分
解油留分より高沸点であつて、かつ沸点330℃以
上の反応生成物が得られるようにおこなう。該反
応生成物は脂肪族オレフインのオリゴマーおよび
脂肪族オレフインと芳香族炭化水素とのアルキレ
ートを主成分とする。反応生成物の沸点が、330
℃より低いか、または該熱分解留分の沸点より低
いときは、工業的価値のない反応生成物となり、
また、酸触媒処理の効果も期待できないので好ま
しくない。
本発明では、上述した如く特定ソースの特定留
分を原料とし、特定の処理をおこなうために、諸
物性に悪影響を及ぼすような高分子量化合物は実
質上生成せず、本発明の反応生成物は比較的低粘
度の、たとえば75℃で3〜20cStの液状物である。
したがつて、通常は酸触媒処理後、未反応留分
(出発原料の熱分解油留分)を蒸留などの物理的
分離手段で分離するのみで、さらにより重質の化
合物を分離することなく反応生成物を使用し得る
ものである。もちろん、用途、その他に応じて該
生成物を適宜の沸点範囲の留分に分割することも
できる。
上記処理により、熱分解油留分のたとえば臭素
価が減少するなど不飽和分が減少しているが、反
応生成物中には、上述した如く脂肪族オレフイン
のオリゴマーが含まれているので、好ましくは接
触水素添加処理をおこなうことにより、実質的に
芳香族核の該水素添加をしないようにしつつ不飽
和分を更に減少もしくは消滅させる。なお、当該
接触水素添加処理に際しては、分離した反応生成
物もしくは該反応生成物を多く含む留分、または
前記酸触媒処理を施した熱分解油留分の混合物そ
のもののいずれかに対してもおこなうことができ
る。
接触水素添加処理には、従来公知のいかなる触
媒も利用できる。たとえば、Pt,Pd,Ni,Co,
Mo,W,Co−Mo,Ni−Wなどの金属系触媒が
使用できる。該処理の条件としては、通常、反応
温度250〜400℃、水素圧20〜100Kg/cm2、水素/
油モル比0.5〜20、LHSV0.1〜10である。
接触水素添加処理後、蒸留などの適宜の手段
で、反応生成物、要すればガス分などが分離す
る。もちろん、用途によつては、該水素添加反応
生成物を適宜の留分にさらに分離しても良い。
このようにして得られた水素添加反応生成物
は、沸点330℃以上、粘度は75℃において25cSt以
下であり、流動点−45℃以下、引火点は140℃以
上である。またその組成は、原料の石油系重質油
の種類、熱分解条件などで、量関係は変動する
が、ノルマルパラフイン類を殆んど含まずに、イ
ソパラフイン類、アルキル置換された単環もしく
は複合環を含む芳香族炭化水素類などから成るも
のである。
また、反応生成物および添加した芳香族炭化水
素を熱分解油留分から分離、取得し除いた残りの
未反応油留分は、ノルマルパラフイン類を多く含
み、さらにイソパラフイン類と少量の芳香族炭化
水素を含むものである。
本発明の特徴をまとめると次の如くである。
(1) 本発明により、重質残油の熱分解プロセスか
らの分解油が高度に利用でき、ひいては工業的
価値が低く、かつ大量に余剰の重質残油を有効
に利用することができるので工業的価値が大き
い。
(2) すなわち、本発明の方法により得られた反応
生成物は、低粘度で、低流動点であり、必要な
らば適宜、接触水素添加処理することにより安
価な電気絶縁油として使用することができる。
また、重質残油を原料としているにもかかわ
らず、金属分や硫黄分は殆ど含まれていない電
気絶縁油が得られる。
(3) 特定ソースの特定組成の留分を原料に特定の
処理をおこなつているので、特に物性に悪影響
をおよぼすような高分子物は実質状生成せず
に、比較的粘度のものが得られるしたがつて、
適宜に、未反応留分を除去するのみで使用でき
るという利点を有する。
次に実施例により本発明を詳述する。
実施例 1
ミナス原油から得られた表1の性状の減圧蒸留
残渣油をコーキングしているデイレードコーキン
グ装置(分解条件;分解温度496℃、滞留時間24
時間、分解圧4Kg/cm2)から表2に示すように、
ガス、コ−クスとともに熱分解油が得られた。
The present invention relates to a method for producing electrical insulating oil, which comprises treating a pyrolysis oil fraction from a pyrolysis process using petroleum heavy residual oil as a raw material. In recent years, due to the depletion of petroleum resources, heavier crude oil has been used, and as a result, the amount of by-product heavy residual oil such as distillation residue oil has also tended to increase.
However, this heavy residual oil has low industrial utility value due to its high viscosity and high sulfur and metal content. On the other hand, the only form of utilization of such heavy residual oil is as a raw material for thermal decomposition processes such as coking. The coking process of this heavy residual oil yields liquid material, ie, pyrolysis oil, along with coke and gas, but the yield of pyrolysis oil in coking is usually quite high, and a large amount of pyrolysis oil fraction can be obtained. It turns out. However, conventional methods for utilizing the pyrolysis oil produced in large quantities have been to perform further processing such as fluidized catalytic cracking, since this oil is relatively rich in aliphatic hydrocarbons and may not have a sufficient octane number. Unless otherwise available, it could not be used as gasoline for automobiles, and could only be used as simple fuel for boilers. Therefore, the utilization of this large amount of pyrolysis oil is becoming a major industrial problem. In view of the above-mentioned circumstances, it is an object of the present invention to produce an excellent electrical insulating oil by treating a large amount of pyrolysis oil fraction obtained as a by-product, which has no utility value other than boiler fuel, in the coking process, for example. It's about getting. By doing so, effective utilization of the pyrolysis oil fraction can be achieved. That is, according to the present invention, heavy petroleum residual oil can be
Electrical insulating oil with low viscosity and low pour point can be obtained by acid-catalyzed treatment of the thermally cracked oil fraction obtained by thermal decomposition at temperatures above 400°C but not exceeding 700°C in the liquid phase. Next, the present invention will be further explained. The petroleum-based heavy residual oil of the present invention refers to atmospheric distillation residue oil, vacuum distillation residue oil, thermal cracking or catalytic cracking residue oil, and various petroleum refining residues such as furfural in the usual sense of the petroleum refining industry. , residual oil extracted with propane, pentane, etc., reformer residual oil, etc., and mixtures thereof. It is necessary that the decomposition temperature of the thermal decomposition process of the present invention is 400°C or higher and does not exceed 600°C.
No thermal decomposition occurs at decomposition temperatures lower than 400℃;
In addition, when the temperature exceeds 600℃, aromatic hydrocarbons, which are themselves highly reactive, become excessive in the resulting pyrolyzed oil regardless of the decomposition time, and high polymers such as resins are removed by acid catalyst treatment. It is not preferable because it is easy to form and the amount of aliphatic olefin having a boiling point in the range of 120 to 290°C is too small. The decomposition temperature is preferably 400-550°C. The decomposition time can be changed as appropriate depending on the main purpose of the thermal decomposition process, such as coke production, viscosity reduction of raw material heavy oil, etc., and can be adopted in the range of 10 seconds to 50 hours, for example. Water vapor or other non-reactive gaseous media can also be present during the decomposition. The decomposition pressure is usually relatively low, at reduced pressure or 50Kg/cm 2
That's about it. Typical thermal cracking processes for heavy residual oil include Hydrocarbon Processing,
As described in Vol. 61, No. 9, September 1982, pp. 160-163, there are the visbreaking method and the coking method. That is, the visbreaking method is a process in which the raw material is thermally decomposed under relatively mild conditions while suppressing the generation of coke in a heating furnace tube, mainly for the purpose of reducing the viscosity of the raw material, and there are two types: a coil type and a soaker type. Normally, cracked oil leaving the cracking furnace is rapidly cooled to crack it and suppress coke. This includes
Examples include the Lummus method and the Shell method. In addition, the coking method is a process that simultaneously produces coke, but after heating the residual oil in a heating furnace for a relatively short period of time, it is sent to a coke drum.
Here, delayed coking (UOP method, Foster
Wheeler method, MWKellogg method, Lummus method and
CONOCO method, etc.), fluid coking method (Exxon method, etc.) in which residual oil is cracked on high-temperature fluid coke, flexi coking method (Exxon method), which combines fluid coking method with gasification process of coke produced, , the EUREKA process, which produces pitch by thermal decomposition and steam stripping at relatively low pressures such as normal pressure. Among these thermal cracking processes, as a result of the sulfur content and metal content in the residual oil being concentrated in the coke produced, the cracked oil contains relatively few impurities.
Therefore, the coking method is preferable because it requires a comparative vessel for purification even after acid catalyst treatment and contains a relatively large amount of aliphatic olefin with a high boiling point. Furthermore, among these, delayed coking is operated on a large scale because it produces lump coke that is useful as a carbon source for graphite for electrodes, and as a result, it produces particularly large amounts of cracked oil as a by-product. Therefore, it is an advantageous caulking method because the benefits will be great if the present invention makes effective use of it. The composition of the pyrolysis oil obtained from the above pyrolysis process varies depending on the type of pyrolysis process, pyrolysis conditions, type of raw heavy oil, etc., but it usually contains almost all aromatic olefins. In addition to paraffins such as normal paraffin and iso-paraffin, it also contains highly reactive aliphatic olefins such as normal olefin and iso-olefin, and also includes alkyl-substituted monocycles such as alkylbenzene, alkylindanes, and alkyltetralins. It includes aromatic hydrocarbons having an alkyl-substituted complex ring such as, and an alkyl-substituted condensed ring such as alkylnaphthalene. Among the pyrolysis oils obtained from the various pyrolysis processes mentioned above, in the present invention, boiling points of 120 to 290
℃, more preferably a pyrolysis oil fraction whose main component is hydrocarbons in the range of 150 to 260℃. A fraction whose main component is a hydrocarbon having a boiling point outside the above range is not preferred because the yield of the reaction product is poor. Furthermore, the pyrolysis oil fraction to be treated in the present invention needs to contain aromatic hydrocarbons and aliphatic olefins. A fraction containing no aromatic hydrocarbons is not preferred because the resulting reaction product will have a high pour point. It is necessary that the aliphatic olefin be contained in the fraction at 10% by weight or more, and a fraction containing less aliphatic olefin is not preferable because the reaction product cannot be recovered in an economical yield. . The typical composition of the target pyrolysis oil fraction is 30 to 70% by weight of paraffin and 10 to 10% of aliphatic olefin.
40% by weight, aromatic hydrocarbons 5-20% by weight.
However, as long as the above-mentioned conditions for the target fraction are satisfied, there is no problem in appropriately fractionating the pyrolysis oil or diluting it with unreacted oil or the like. As the acid catalyst used in the treatment, solid acid catalysts, mineral acids, so-called Friedel-Crafts catalysts, organic acids, etc. are preferably used. For example, specifically, acid clay minerals such as acid clay and activated clay, amorphous or crystalline silica-alumina, AlF 3 .
Al 2 O 3 , solid acid catalysts such as strong acid type ion exchange resins, HF, AlCl 3 , BF 3 . Friedel-Crafts catalysts such as CnCl4 , inorganic or organic acids such as sulfuric acid, para-toluenesulfonic acid, trifluoromethanesulfonic acid. The reaction format of the treatment may be batch type, semi-batch type or flow type, but when using a solid acid, it is preferable to use flow type. The above-mentioned acid catalyst is added to the fraction in an amount of 0.2 to 20% by weight, preferably 1 to 10% by weight in a batch process, and treated at an LHSV of 0.1 to 20, preferably 0.5 to 10 in a flow process. do. Reaction temperature is 30-330
℃, preferably 50 to 250℃. Although the treatment time varies depending on the reaction conditions, that is, the amount of catalyst, reaction temperature, raw material composition, etc., a sufficient time is required for the reaction to be completed, and can usually be selected within the range of 2 to 24 hours. The reaction pressure may be any pressure necessary to maintain the reaction phase in a liquid phase. In the present invention, the acid catalyst treatment is carried out in such a manner that a reaction product having a boiling point higher than that of the pyrolysis oil fraction and a boiling point of 330° C. or higher is obtained. The reaction product is mainly composed of oligomers of aliphatic olefins and alkylates of aliphatic olefins and aromatic hydrocarbons. The boiling point of the reaction product is 330
℃ or lower than the boiling point of the thermal decomposition fraction, the reaction product is of no industrial value;
Further, the effect of acid catalyst treatment cannot be expected, which is not preferable. In the present invention, as mentioned above, a specific distillate from a specific source is used as a raw material and a specific treatment is performed, so that high molecular weight compounds that adversely affect various physical properties are not substantially generated, and the reaction product of the present invention is It is a liquid material with a relatively low viscosity, for example, 3 to 20 cSt at 75°C. Therefore, after acid catalyst treatment, the unreacted fraction (thermal cracked oil fraction of the starting material) is usually separated by physical separation means such as distillation, without further separating heavier compounds. The reaction product can be used. Of course, the product can also be divided into fractions with appropriate boiling point ranges depending on the use and other purposes. Through the above treatment, the unsaturated content of the pyrolysis oil fraction is reduced, for example, the bromine number is reduced, but the reaction product contains oligomers of aliphatic olefins as described above, so it is preferable. By carrying out a catalytic hydrogenation treatment, unsaturation is further reduced or eliminated while substantially avoiding hydrogenation of aromatic nuclei. The catalytic hydrogenation treatment may also be performed on either the separated reaction product, a fraction containing a large amount of the reaction product, or the mixture itself of the pyrolysis oil fraction subjected to the acid catalyst treatment. be able to. Any conventionally known catalyst can be used for the catalytic hydrogenation treatment. For example, Pt, Pd, Ni, Co,
Metal catalysts such as Mo, W, Co-Mo, and Ni-W can be used. The conditions for this treatment are usually a reaction temperature of 250 to 400°C, a hydrogen pressure of 20 to 100 Kg/cm 2 , and a hydrogen/
Oil molar ratio is 0.5-20, LHSV 0.1-10. After the catalytic hydrogenation treatment, reaction products and, if necessary, gas components are separated by appropriate means such as distillation. Of course, depending on the application, the hydrogenation reaction product may be further separated into appropriate fractions. The hydrogenation reaction product thus obtained has a boiling point of 330°C or higher, a viscosity of 25 cSt or lower at 75°C, a pour point of -45°C or lower, and a flash point of 140°C or higher. The composition varies depending on the type of raw petroleum heavy oil, thermal decomposition conditions, etc., but it contains almost no normal paraffins, isoparaffins, alkyl-substituted monocyclic rings, or It consists of aromatic hydrocarbons containing complex rings. In addition, the unreacted oil fraction that remains after the reaction products and added aromatic hydrocarbons are separated and removed from the pyrolysis oil fraction contains a large amount of normal paraffins, and isoparaffins and a small amount of aromatic carbonization. Contains hydrogen. The features of the present invention are summarized as follows. (1) According to the present invention, the cracked oil from the pyrolysis process of heavy residual oil can be utilized to a high degree, and the industrial value is low, and a large amount of surplus heavy residual oil can be effectively utilized. It has great industrial value. (2) That is, the reaction product obtained by the method of the present invention has a low viscosity and a low pour point, and can be used as an inexpensive electrical insulating oil by subjecting it to catalytic hydrogenation treatment if necessary. can. Furthermore, even though heavy residual oil is used as a raw material, electrical insulating oil containing almost no metal content or sulfur content can be obtained. (3) Since the raw material is a fraction of a specific composition from a specific source and subjected to specific processing, products with relatively high viscosity are obtained without substantially producing polymeric substances that would adversely affect physical properties. As a result,
It has the advantage that it can be used only by removing unreacted fractions as appropriate. Next, the present invention will be explained in detail with reference to Examples. Example 1 Delayed coking equipment coking vacuum distillation residue oil with properties shown in Table 1 obtained from Minas crude oil (decomposition conditions: decomposition temperature 496°C, residence time 24
time, decomposition pressure 4Kg/cm 2 ), as shown in Table 2,
Pyrolysis oil was obtained along with gas and coke.
【表】【table】
【表】
本実施例においては、上記表2の熱分解油留分
中、留分2を原料として用いたが、その組成は表
3に示した。[Table] In this example, fraction 2 of the pyrolysis oil fractions shown in Table 2 was used as a raw material, and its composition is shown in Table 3.
【表】
次に4の留分2に40gのAlCl3を加え、50℃
で20時間、攪拌しつつバツチ式で処理した。処理
後、反応混合物をアンモニア水で処理し、AlCl3
を中和分解し、水洗除去した。次に脱水し、340
℃+の留分として反応生成物(870g、収率29%)
を得た。この反応生成物の臭素価が6.4cg/gで
あつて、芳香族分は78.7%で残りは殆どオレフイ
ンオリゴマーであつた。
続いて、この反応生成物を、Cp−Mo触媒を用
いて水素圧50Kg/cm2、反応温度280℃、1原料油
容量/触媒容量/hrの条件で水素添加処理した。
水素添加後、分解生成した軽質分を留去し、水
素添加処理された反応生成物を回収した。回収率
は92%であつた。この水素添加処理された反応生
成物は、臭素価0.34cg/gであり、芳香族分は
76.6%であつて、芳香族化合物の核水素化は実質
的におこつていなかつた。
この水素添加処理された反応生成物の物性及び
ASTMD−1934に準拠した電気特性試験と、JIS
C2101に準拠した酸化安定度試験の結果は表4の
まとめて示す。なお、比較のため表4には鉱油の
結果もあわせて示した。
表4の結果から、本発明の水素化反応生成物
は、鉱油と比較しても優れた物性を有することが
明らかなので電気絶縁油に最適である。[Table] Next, 40g of AlCl 3 was added to fraction 2 of 4, and the mixture was heated to 50°C.
The mixture was treated in batches for 20 hours with stirring. After treatment, the reaction mixture was treated with aqueous ammonia and AlCl 3
was neutralized and decomposed and removed by washing with water. Then dehydrate and 340
Reaction product (870 g, 29% yield) as a fraction at + °C
I got it. The bromine number of this reaction product was 6.4 cg/g, the aromatic content was 78.7%, and the remainder was mostly olefin oligomers. Subsequently, this reaction product was subjected to hydrogenation treatment using a Cp-Mo catalyst at a hydrogen pressure of 50 Kg/cm 2 , a reaction temperature of 280° C., and a ratio of 1 raw oil volume/catalyst volume/hr. After hydrogenation, light components produced by decomposition were distilled off, and the hydrogenated reaction product was recovered. The recovery rate was 92%. This hydrogenated reaction product has a bromine value of 0.34 cg/g and an aromatic content of
It was 76.6%, and nuclear hydrogenation of aromatic compounds did not substantially occur. Physical properties of this hydrogenated reaction product and
Electrical property test based on ASTMD-1934 and JIS
The results of the oxidation stability test according to C2101 are summarized in Table 4. For comparison, Table 4 also shows the results for mineral oil. From the results in Table 4, it is clear that the hydrogenation reaction product of the present invention has superior physical properties compared to mineral oil, and is therefore most suitable as an electrical insulating oil.
【表】
実施例 2
実施例1で得られた表2の留分2、4に40ml
のBF3・H2Oを加え50℃で2時間バツチ式で処
理した。
反応混合物をアンモニア水溶液で処理し、触媒
を中和水洗除去した。充分脱水後、350℃+の留分
として反応生成物690gを回収した。この生成物
は、粘度10.2cSt(75℃)、流動点−47.5℃、引
火点200℃であつた。
実施例 3
実施例1のミナス減圧残油を、滞留時間1.5時
間、温度48.5℃、圧力1.5Kg/cm2の条件下で熱分
解し、生成した熱分解油を精留し、100〜300℃の
沸点範囲の熱分解油留分(120〜290℃の成分は85
%含んでいる)を得た。得率は37%であつた。
この熱分解油留分を、シリカ・アルミナを触媒
として、反応温度200℃、原料油1容量/触媒
量/Hrの条件で、固定床流通式で処理した。
反応液はそのままCo−Mo触媒を用いて水素圧
50Kg/cm2、反応温度300℃、原料油1容量/触媒
容量/Hr、H2/油モル比10の条件で接触水素添
加処理をおこなつた。
水素添加処理後、330℃+の留分として反応生成
物を得た。
この水素添加処理生成物は粘度5.4cSt(75
℃)、流動点−52.5℃、引火点152℃であつた。
続いて、水素添加処理された反応生成物につい
ても、電気特性、酸化安定度について試験した。
表5にその結果を示す。
なお、実施例2の350℃+の反応生成物も同様に
水素添加処理したもので、その試験結果もあわせ
て示す。[Table] Example 2 Add 40 ml to fractions 2 and 4 of Table 2 obtained in Example 1.
of BF 3 .H 2 O was added thereto and treated in batches at 50° C. for 2 hours. The reaction mixture was treated with ammonia aqueous solution, and the catalyst was neutralized and removed by washing with water. After sufficient dehydration, 690 g of the reaction product was recovered as a 350°C + fraction. The product had a viscosity of 10.2 cSt (75°C), a pour point of -47.5°C and a flash point of 200°C. Example 3 The Minas vacuum residual oil from Example 1 was thermally decomposed under the conditions of a residence time of 1.5 hours, a temperature of 48.5℃, and a pressure of 1.5Kg/ cm2 , and the resulting thermal decomposition oil was rectified and heated to a temperature of 100 to 300℃. Pyrolysis oil fraction with a boiling point range of (120-290℃ is 85℃)
%) was obtained. The yield rate was 37%. This pyrolysis oil fraction was treated in a fixed bed flow system using silica/alumina as a catalyst at a reaction temperature of 200° C. and at a ratio of 1 volume of raw oil/amount of catalyst/Hr. The reaction solution is directly exposed to hydrogen pressure using a Co-Mo catalyst.
Catalytic hydrogenation treatment was carried out under the following conditions: 50 Kg/cm 2 , reaction temperature 300° C., 1 volume of raw oil/capacity of catalyst/Hr, and H 2 /oil molar ratio of 10. After the hydrogenation treatment, the reaction product was obtained as a 330°C + fraction. This hydrogenated product has a viscosity of 5.4 cSt (75
), pour point -52.5°C, and flash point 152°C. Subsequently, the hydrogenated reaction product was also tested for electrical properties and oxidation stability.
Table 5 shows the results. The reaction product of Example 2 at 350° C. + was also subjected to hydrogenation treatment, and the test results are also shown.
Claims (1)
して沸点が120〜290℃の範囲にある炭化水素を主
成分とし、かつ芳香族炭化水素と少なくとも10重
量%の脂肪族オレフインとを含む熱分解油留分を
得、これを酸触媒存在下、液相で、反応温度30〜
330℃で処理することにより沸点330℃以上の反応
生成物を生成せしめることを特徴とする電気絶縁
油の製造法。 2 前記熱分解プロセスがコーキングプロセスで
ある特許請求の範囲第1項記載の方法。 3 石油系重質残油を400〜600℃の温度で熱分解
して沸点が120〜290℃の範囲にある炭化水素を主
成分とし、かつ芳香族炭化水素と少なくとも10重
量%の脂肪族オレフインとを含む熱分解油留分を
得、これを酸触媒存在下、液相で、反応温度30〜
330℃で処理することにより沸点330℃以上の反応
生成物を得、次いで芳香族炭化水素の核水素化が
実質的に生じない条件で接触水素添加処理するこ
とを特徴とする電気絶縁油の製造法。 4 前記熱分解プロセスがコーキングである特許
請求の範囲第3項記載の方法。[Claims] 1. The main component is a hydrocarbon whose boiling point is in the range of 120 to 290 degrees Celsius obtained by thermally decomposing petroleum heavy residual oil at a temperature of 400 to 600 degrees Celsius, and aromatic hydrocarbons and at least 100 degrees Celsius. A pyrolysis oil fraction containing % by weight of aliphatic olefins was obtained, and this was heated in the liquid phase in the presence of an acid catalyst at a reaction temperature of 30~30°C.
A method for producing electrical insulating oil characterized by producing a reaction product with a boiling point of 330°C or higher by processing at 330°C. 2. The method of claim 1, wherein the pyrolysis process is a coking process. 3 Petroleum heavy residual oil is pyrolyzed at a temperature of 400 to 600°C, and the main component is hydrocarbons with boiling points in the range of 120 to 290°C, and aromatic hydrocarbons and at least 10% by weight of aliphatic olefins. A pyrolysis oil fraction containing
Production of electrical insulating oil characterized by obtaining a reaction product with a boiling point of 330°C or higher by processing at 330°C, and then subjecting it to catalytic hydrogenation treatment under conditions that substantially do not cause nuclear hydrogenation of aromatic hydrocarbons. Law. 4. The method of claim 3, wherein the pyrolysis process is coking.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2184984A JPS60167204A (en) | 1984-02-10 | 1984-02-10 | Electrically insulating oil |
US06/698,327 US4755275A (en) | 1984-02-10 | 1985-02-05 | Electrical insulating oil |
EP85300869A EP0153112B1 (en) | 1984-02-10 | 1985-02-08 | Electrical insulating oil |
CA000473942A CA1261615A (en) | 1984-02-10 | 1985-02-08 | Electrical insulating oil |
DE8585300869T DE3568284D1 (en) | 1984-02-10 | 1985-02-08 | Electrical insulating oil |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2184984A JPS60167204A (en) | 1984-02-10 | 1984-02-10 | Electrically insulating oil |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS60167204A JPS60167204A (en) | 1985-08-30 |
JPH0438084B2 true JPH0438084B2 (en) | 1992-06-23 |
Family
ID=12066544
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2184984A Granted JPS60167204A (en) | 1984-02-10 | 1984-02-10 | Electrically insulating oil |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS60167204A (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS53127700A (en) * | 1977-04-13 | 1978-11-08 | Nippon Petrochemicals Co Ltd | Composition for electric insulating oil |
-
1984
- 1984-02-10 JP JP2184984A patent/JPS60167204A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS53127700A (en) * | 1977-04-13 | 1978-11-08 | Nippon Petrochemicals Co Ltd | Composition for electric insulating oil |
Also Published As
Publication number | Publication date |
---|---|
JPS60167204A (en) | 1985-08-30 |
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