JPH0438083B2 - - Google Patents
Info
- Publication number
- JPH0438083B2 JPH0438083B2 JP59021850A JP2185084A JPH0438083B2 JP H0438083 B2 JPH0438083 B2 JP H0438083B2 JP 59021850 A JP59021850 A JP 59021850A JP 2185084 A JP2185084 A JP 2185084A JP H0438083 B2 JPH0438083 B2 JP H0438083B2
- Authority
- JP
- Japan
- Prior art keywords
- oil
- fraction
- boiling point
- pyrolysis
- oil fraction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003921 oil Substances 0.000 claims description 119
- 238000000034 method Methods 0.000 claims description 51
- 238000000197 pyrolysis Methods 0.000 claims description 51
- 238000009835 boiling Methods 0.000 claims description 29
- 239000006227 byproduct Substances 0.000 claims description 27
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 21
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 20
- -1 aliphatic olefins Chemical class 0.000 claims description 19
- 239000003208 petroleum Substances 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 19
- 239000007795 chemical reaction product Substances 0.000 claims description 16
- 238000004939 coking Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 239000003377 acid catalyst Substances 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 239000010735 electrical insulating oil Substances 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 4
- 238000002407 reforming Methods 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000000354 decomposition reaction Methods 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 239000000571 coke Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 238000001833 catalytic reforming Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 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
- 238000005336 cracking Methods 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 3
- 238000000638 solvent extraction Methods 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
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-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
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 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
- 150000001993 dienes Chemical class 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 238000005292 vacuum distillation 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
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 210000003918 fraction a Anatomy 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000002309 gasification Methods 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
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- DBJYYRBULROVQT-UHFFFAOYSA-N platinum rhenium Chemical compound [Re].[Pt] DBJYYRBULROVQT-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 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
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Lubricants (AREA)
- Organic Insulating Materials (AREA)
Description
本発明は石油系重質残油の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車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、
この多量に副生する熱分解油の利用は工業上の大
きな問題となりつつある。
ところで、ナフサの如き石油系軽質炭化水素を
750〜850℃で熱分解することにより、エチレン、
プロピレンなどの石油科学工業の基礎原料を製造
することは、いわゆるナフサクラツキングとして
広く行なわれている。この際、熱分解装置へ供給
する原料油の種類、分解条件などによつて異なる
ため一概には言えないが、エチレン生産量に対
し、芳香族炭化水素を多く含む熱分解副生油が
0.5〜3.0重量%副生する。
またオクタン価を向上させるためや、ベンゼ
ン、トルエン、キシレンなどの芳香族炭化水素含
量を増大させて芳香族炭化水素を得るために、ナ
フサなどを水素存在下でPtまたはPt−Re/Al2
O3の如き貴金属触媒と接触させる接触改質から
大量に得られる改質油も、当然ながら芳香族炭化
水素が多く含まれている。
さらに、上記の熱分解副生油や改質油から、溶
剤抽出などの分離手段により、ベンゼン、トルエ
ンおよびキシレンが分離除去された残油は、C9,
C10などの芳香族炭化水素を主とする留分ではあ
るが、多数の成分の混合物であつて、各成分への
分離が困難であるなどの理由で従来より、その工
業的な利用が十分ではない。
本発明者らは、上述の如き工業的な利用が十分
ではないが留分の有効利用をはかるべく鋭意研究
した結果、重質残油の熱分解から得られる熱分解
油留分に、熱分解副生油留分、改質油および熱分
解副生油留分や改質油からの芳香族残油などを混
合した原料を酸触媒処理をすることにより電気絶
縁油に敵した低温特性の優れた高沸点留分が得ら
れることを見出し本発明を完成させたものであ
る。
すなわち、本発明は、(A)石油系重質残油を400
℃以上、600℃を越えない温度で熱分解する熱分
解プロセスから得られる熱分解油留分であつて、
沸点120〜290℃の範囲にある炭化水素を主成分と
し、かつ脂肪族オレフインを含む熱分解油留分20
〜95重量%と、(B)(a)石油系軽質油を温度750〜850
℃で熱分解し、次いで不飽和分を減少させる処理
を施して得られた熱分解副生油留分、(b)沸点50〜
250℃の石油系軽質油を接触改質し、次いで必要
に応じて不飽和分を減少させる処理を施して得ら
れる改質油留分、および(c)上記(a)の熱分解副生油
および/または(b)の改質油留分を原料として、分
離取得される芳香族炭化水素を主とする芳香族留
分からなる群から選ばれる1種または2種以上の
沸点150〜250℃の留分80〜5重量%とを、酸接触
存在下、液相で、反応温度30〜330℃で処理する
ことにより優れた低温特性を有する沸点315℃以
上の反応生成物からなる事を特徴とする電気絶縁
油に関する。
本発明の(A)項の熱分解すべき石油系重質残油と
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、ベ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、得られた熱分解油中に、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、過熱炉チユ
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物が少なく、
したがつて、酸触媒処理後も精製が比較容器であ
る。また高沸点に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
分とする留分では工業的に有用な反応生成物が得
られないので好ましくない。また、本発明の処理
すべき熱分解油留分は、脂肪族オレフインを含む
ことが必要である。
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。
上記(A)項の熱分解油留分に混合すべき前記(B)項
の成分としての(a)熱分解副生油留分、(b)の改質油
留分および(c)の芳香族留分は次のようなものであ
る。
すなわち、(a)の熱分解副生油留分は、エチレ
ン、プロプレンなどの製造を目的として石油系軽
質油を温度750〜840℃で熱分解する際に得られる
熱分解副生油留分であつて、ジオレフインやモノ
オレフインなどの不飽和を減少させる処理が施さ
れた留分である。
石油系軽質油としてはナフサ、灯軽油、LPG、
ブタンなどの各種石油系軽質油があげられる。得
られる熱分解副生油留分の性状を考慮すると、熱
分解原料としてはナフサ、灯軽油が本発明の目的
により適合するので好ましい。
熱分解法については、特に限定はなく、通常行
なわれている750〜850℃における各種の熱分解
法、たとえば、管状の分解炉を使用する管状分解
炉法、熱分解を用いる熱媒体分解法などが適宜利
用できる。
この熱分解による生成物から、目的生成物であ
るエチレン、プロピレン、ブタジエンなどのオレ
フイン、ジオレフインンなどを除いた熱分解副生
油留分は、原料である石油系軽質油の種類、熱分
解条件などによつて異なるものであるが、芳香族
炭化水素を比較的多くの含み、パラフイン類2〜
10重量%、ナフテン類3〜10重量%、芳香族炭化
水素55〜85重量%、脂肪族オレフイン2〜10重量
%、芳香族オレフイン2〜15重量%の範囲で変動
する炭素数6〜10の留分である。このうち、本発
明においては沸点150〜280℃の留分を前記(A)の熱
分解油留分に混合して用いる。
但し、本発明の熱分解副生油留分はさらに不飽
和分を0.5%以下、好ましくは0.1%以下に減少さ
せる処理が施された留分である。該処理は、従来
公知の接触水素添加処理によつて達成される。た
とえばPt,Pd,Ni,Co,Mo,W,Co−Mo,
Ni−Wなどの金属接触あるいは、これらをアル
ミナなどの担体に担持させた触媒を用いることが
できる。該処理の条件としては、通常、反応温度
200〜400℃、水素圧20〜150Kg/cm2、水素/油モ
ル比0.5〜20,LHSV0.1〜10である。
また前記(b)の改質油留分とは、沸点50〜250℃
の石油系軽質油、たとえば直留ナフサなどのナフ
サを接触改質して得られる改質油留分である。接
触改質は、オクタン価を向上させるためや、ベン
ゼン、トルエン、キシレンなどを得るために石油
精製や石油化学の分野で広くおこなわれている。
この接触改質は、水素の存在下反応温度450〜510
℃でおこなわれ、触媒としてはアルミナもしくは
シリカ−アルミナ担持の白金、白金−レニウム、
酸化モリブデン、酸化クロムなどの金属触媒であ
る。工業的な方法では、固定床式であるUOPの
プラツトホーミング、スタンダード・オイル・カ
ンパニーのウルトラホーミングなどがあり、その
ほか、流動床式、移動式などの形式もある。接触
改質では、主に脱水素、環化反応が起り、そのほ
か、異性化反応などもおこり、その結果、ベンゼ
ン、トルエン、キシレンなどのBTX含量が増大
し、オクタン価が向上する。しかしながら、得ら
れる改質油は前記(A)の熱分解副生油などと比較
し、臭素価が約3.8以下と不飽和分が非常に少な
いのが特徴である。より好ましい改質油の臭素価
は約2以下である。
この接触改質油留分の代表組成は、パラフイン
30〜35重量%、芳香族炭化水素65〜70重量%、オ
レフイン類0〜2重量%の範囲で変動する炭素数
6〜10の留分である。本発明においては、沸点
150〜280℃の接触改質油留分を用いる。
上述した如く、該留分は不飽和分が通常少ない
が、必要に応じて、不飽和を減少させる処理を施
すことができる。該処理は前述の(a)の熱分解副生
油の不飽和分を減少させる処理と同様にしておこ
なうことができる。
さらに、これら接触改質油や、前記熱分解副生
油もしくは、これらの混合物を原料とし、適宜の
分離手段により得られた芳香族炭化水素を主とす
る芳香族留分を前記(c)の芳香族留分として使用で
きる。この分離は、石油化学の分野において、接
触改質油や熱分解副生油からBTXを得るために
大規模におこなわれており、通常は、溶剤抽出法
かまたは抽出蒸留法によりおこなわれている。代
表的な溶剤抽出法には、抽出溶剤としてジエチレ
ングリコールやトリエチレングリコールなどを用
いるユデツクス法(DOW法)、スルホランを用
いるスルホラン法(Shell法)などがある。なお、
この抽出においては、不飽和分の重合による装置
の閉塞をさけるために、通常は前処理として水素
添加などにより不飽和分の除去がなされる。
このように、接触改質油や熱分解副生油から分
離して得られる芳香族炭化水素を主とする芳香族
留分のうち、沸点150〜250℃の留分(本発明の(c)
の芳香族留分)は、炭素数9〜10の炭化水素から
なるが、アルキルベンゼン、ポリアルキルベンゼ
ン、ナフタレンそのほか多くの芳香族炭化水素を
主に含んでおり、従来よりこの沸点範囲の留分
は、BTX留分とともに多量に得られるにもかか
わらず、有効な利用方法がなかつたものである。
本発明においては、(A)の熱分解油留分に、(B)の
(a)熱分解副生油留分、(b)改質油留分および(c)芳香
族留分を混合し、酸触媒処理をする。(a)〜(c)の留
分は適宜混合し、(B)の留分として用いることがで
きる。両者の混合割合は(A)の熱分解油留分20〜95
重量%、(B)の留分80〜5重量%である。得られた
反応生成物を電気絶縁油として用いるときは、低
温特性が優れたものが得られるので、より好まし
い混合割合は、(A)の留分70〜90重量%、Bの留分
30〜10重量%である。
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.SnCl4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。
上気した酸触媒を当該留分に大して、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〜
300℃、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
成などのよつて異なるが、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。反応圧力は液相を保つに必要な圧力
であれば良い。
本発明においては、上記酸触媒処理を、沸点
315℃以上の反応生成物が得られるようにおこな
う。該反応生成物は主として脂肪族オレフインが
反応したものであつて、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ものである。沸
点が315℃より低い反応生成物では引火点等が低
くなり絶縁油として価値がなく、また酸触媒処理
をした意味も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組
成の留分を原料とし、特定の処理をおこなつてい
るので、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
比較的低粘度である。したがつて、用途によつて
は未反応留分(原料留分)を、たとえば蒸留によ
つて分離するのみで、さらに重質留分を分離する
ことなく絶縁油として使用できるのである。もち
ろん、必要に応じ該生成物を適宜の沸点範囲留分
に分割することができる。
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、不飽和分を
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そのもののおずれに対
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。この水素
添加処理は、上記芳香族炭化水素の各水素化が実
質的に生じない条件で行なう。
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、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315℃以上、粘度は75℃において25cst以
下であり、流動点−40℃以下、引火点は140℃以
上である。またその組成は原料の沸点範囲、混合
割合等によつて変動するが、ノルマルパラフイン
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。
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
らの分解油および石油系軽質油の熱分解副生
油、または接触改質ガソリン中の高沸点留分
(bp150〜250℃)が高度に利用できる。すなわ
ち工業的価値が低く、かつ大量に余剰の重質残
油の有効利用が達成できるので、工業的価値が
大きい。同時に、付加価値の高いベンゼン、ト
ルエン、キシレン等製造の際に副生される工業
的価値の低い高沸点留分を利用して工業的価値
の高い製品が得られる。
(2) 特定原料の特定組織の留分を原料にして特定
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量物は実質上生成せ
ず、比較的低粘度のものが得られる。したがつ
て、可能ならば、未反応油留分を留分するのみ
で安価な電気絶縁油として使用できるという利
点を有する。
また、重質残油からの熱分解油を原料としてい
るにもかかわらず、不飽和分、金属分および硫黄
分などが少ない電気絶縁油が得られる。
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するデイレードコーキング装
置(分解温度496℃、滞留時間24時間、分解圧4
Kg/cm2)表2に示す収率で、ガス、コ−クスとと
もに熱分解油が得られた。このうち、沸点160〜
260℃の留分を留分Aとし、その組成を表3に示
す。
The present invention relates to a method for producing electrical insulating oil, which comprises treating a pyrolysis oil fraction from a pyrolysis process of petroleum heavy residual oil. 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 normal coking is quite high, and a large amount of pyrolysis oil can be obtained. Become. 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 by-product pyrolysis oil is becoming a major industrial problem. By the way, petroleum-based light hydrocarbons such as naphtha
By pyrolysis at 750-850℃, ethylene,
The production of basic raw materials for the petrochemical industry, such as propylene, is widely practiced as so-called naphtha cracking. At this time, it is difficult to make a general statement because it varies depending on the type of feedstock oil supplied to the pyrolysis equipment, cracking conditions, etc., but the amount of pyrolysis by-product oil containing a large amount of aromatic hydrocarbons is relative to the amount of ethylene produced.
0.5 to 3.0% by weight is produced as a by-product. In addition, in order to improve the octane number or to obtain aromatic hydrocarbons by increasing the content of aromatic hydrocarbons such as benzene, toluene, and xylene, naphtha and the like are converted into Pt or Pt-Re/Al 2 in the presence of hydrogen.
The reformed oil obtained in large quantities from catalytic reforming in which it is brought into contact with a noble metal catalyst such as O 3 naturally also contains a large amount of aromatic hydrocarbons. Furthermore, residual oil from which benzene, toluene, and xylene are separated and removed from the above-mentioned thermal decomposition by-product oil and reformed oil by separation means such as solvent extraction is C 9 ,
Although it is a distillate mainly composed of aromatic hydrocarbons such as C10 , its industrial use has not been sufficient due to the fact that it is a mixture of many components and it is difficult to separate each component. isn't it. As a result of intensive research into the effective use of fractions, which are not fully utilized industrially as described above, the inventors of the present invention have found that the pyrolysis oil fraction obtained from the pyrolysis of heavy residual oil has been Excellent low-temperature properties comparable to electrical insulating oils are obtained through acid catalyst treatment of raw materials that are a mixture of by-product oil fractions, reformed oils, pyrolysis by-product oil fractions, and aromatic residual oils from reformed oils. The present invention was completed by discovering that a high boiling point fraction can be obtained. That is, the present invention provides (A) 400% petroleum-based heavy residual oil.
A pyrolysis oil fraction obtained from a pyrolysis process that is thermally decomposed at temperatures above ℃ but not exceeding 600℃,
Pyrolysis oil fraction 20 whose main component is hydrocarbons with a boiling point in the range of 120 to 290℃ and also contains aliphatic olefins.
~95% by weight and (B) (a) petroleum light oil at a temperature of 750 to 850.
Pyrolysis by-product oil fraction obtained by pyrolysis at ℃ and then treatment to reduce unsaturation, (b) boiling point 50~
A reformed oil fraction obtained by catalytically reforming light petroleum oil at 250°C and then optionally undergoing treatment to reduce unsaturated content, and (c) the pyrolysis byproduct oil of (a) above. and/or one or more aromatic fractions with a boiling point of 150 to 250°C selected from the group consisting of aromatic fractions mainly containing aromatic hydrocarbons separated and obtained from the reformed oil fraction of (b) as a raw material. It is characterized by forming a reaction product with a boiling point of 315°C or higher that has excellent low-temperature properties by treating a fraction of 80 to 5% by weight in the liquid phase in the presence of acid contact at a reaction temperature of 30 to 330°C. Regarding electrical insulating oil. The petroleum heavy residual oil to be thermally cracked in item (A) of the present invention refers to atmospheric distillation residue oil, vacuum distillation residue oil, thermal cracking or catalytic cracking residue oil, and various Refers to petroleum refining residues such as furfural, propane, bentane extraction residues, reformer residues, 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 acid-catalyzed treatment results in high polymers such as resin components. This is not preferable because it tends to result in the formation of olefins and the amount of aliphatic olefins with boiling points 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 superheating 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 fluidized coke, flexi coking method (Exxon method), which combines fluid coking method with gasification process of produced coke, , 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 produced coke, the cracked oil contains relatively few of these impurities.
Therefore, purification after acid catalytic treatment is also a comparative vessel. Further, the coking method is preferable because the high boiling point contains a relatively large amount of aliphatic olefin. 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 of the above range is not preferred because an industrially useful reaction product cannot be obtained. Furthermore, the pyrolysis oil fraction to be treated in the present invention needs to contain aliphatic olefins. 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. (a) Pyrolysis by-product oil fraction, (b) reformed oil fraction, and (c) aroma as the components of section (B) to be mixed with the pyrolysis oil fraction of section (A) above. The group fractions are as follows. That is, the pyrolysis by-product oil fraction (a) is a pyrolysis by-product oil fraction obtained when petroleum light oil is pyrolyzed at a temperature of 750 to 840°C for the purpose of producing ethylene, proprene, etc. In particular, it is a distillate that has been treated to reduce unsaturation such as diolefins and monoolefins. Petroleum-based light oils include naphtha, kerosene, LPG,
Examples include various petroleum light oils such as butane. Considering the properties of the resulting thermal decomposition by-product oil fraction, naphtha and kerosene are preferred as the thermal decomposition raw materials because they are more suitable for the purpose of the present invention. There are no particular limitations on the thermal decomposition method, and various commonly used thermal decomposition methods at 750 to 850°C, such as a tubular decomposition furnace method using a tubular decomposition furnace, a thermal medium decomposition method using pyrolysis, etc. can be used as appropriate. The thermal decomposition byproduct oil fraction, which is obtained by removing the target products such as olefins and diolefins such as ethylene, propylene, and butadiene, from the products of this thermal decomposition is determined by the type of petroleum light oil used as the raw material, the thermal decomposition conditions, etc. It contains a relatively large amount of aromatic hydrocarbons, and contains paraffins 2 to
10% by weight of naphthenes, 3-10% by weight of naphthenes, 55-85% by weight of aromatic hydrocarbons, 2-10% by weight of aliphatic olefins, 2-15% by weight of aromatic olefins with a carbon number of 6-10. It is a distillate. Among these, in the present invention, a fraction with a boiling point of 150 to 280° C. is used by mixing it with the thermally cracked oil fraction of (A). However, the thermal decomposition byproduct oil fraction of the present invention is a fraction that has been further treated to reduce the unsaturated content to 0.5% or less, preferably 0.1% or less. This treatment is achieved by a conventionally known catalytic hydrogenation treatment. For example, Pt, Pd, Ni, Co, Mo, W, Co-Mo,
A metal contact such as Ni-W or a catalyst in which these are supported on a carrier such as alumina can be used. The conditions for this treatment are usually the reaction temperature
200-400°C, hydrogen pressure 20-150 Kg/cm 2 , hydrogen/oil molar ratio 0.5-20, and LHSV 0.1-10. In addition, the reformed oil fraction in (b) above has a boiling point of 50 to 250°C.
It is a reformed oil fraction obtained by catalytically reforming light petroleum oil, such as naphtha such as straight-run naphtha. Catalytic reforming is widely used in the oil refining and petrochemical fields to improve octane number and to obtain benzene, toluene, xylene, etc.
This catalytic reforming is carried out in the presence of hydrogen at a reaction temperature of 450-510°C.
The catalyst is platinum supported on alumina or silica-alumina, platinum-rhenium,
Metal catalysts such as molybdenum oxide and chromium oxide. Industrial methods include fixed-bed UOP platform homing and Standard Oil Company's ultrahoming, as well as fluidized bed and mobile methods. In catalytic reforming, dehydrogenation and cyclization reactions mainly occur, as well as isomerization reactions, which increase the content of BTX such as benzene, toluene, and xylene, and improve the octane number. However, the resulting reformed oil is characterized by having a bromine number of about 3.8 or less and a very low unsaturated content compared to the thermal decomposition by-product oil of (A). A more preferred reformate has a bromine number of about 2 or less. The typical composition of this catalytic reforming oil fraction is paraffin
30-35% by weight, 65-70% by weight of aromatic hydrocarbons, and 0-2% by weight of olefins. In the present invention, the boiling point
A catalytic reforming oil fraction of 150-280°C is used. As mentioned above, the fraction usually has a low amount of unsaturation, but if necessary, it can be treated to reduce unsaturation. This treatment can be carried out in the same manner as the treatment for reducing the unsaturated content of the thermal decomposition by-product oil (a) described above. Furthermore, using these catalytically reformed oils, the pyrolysis by-product oils, or mixtures thereof as raw materials, an aromatic fraction mainly composed of aromatic hydrocarbons obtained by an appropriate separation means is used as described in (c) above. Can be used as an aromatic fraction. This separation is carried out on a large scale in the field of petrochemistry to obtain BTX from catalytic reforming oil or pyrolysis by-product oil, and is usually carried out by solvent extraction or extractive distillation. . Typical solvent extraction methods include the Udex method (DOW method), which uses diethylene glycol, triethylene glycol, etc. as an extraction solvent, and the sulfolane method (Shell method), which uses sulfolane. In addition,
In this extraction, in order to avoid blockage of the apparatus due to polymerization of unsaturated components, unsaturated components are usually removed by hydrogenation or the like as a pretreatment. In this way, among the aromatic fractions mainly consisting of aromatic hydrocarbons obtained by separation from catalytic reforming oil and pyrolysis byproduct oil, the fraction with a boiling point of 150 to 250°C ((c) of the present invention)
(aromatic fraction) consists of hydrocarbons having 9 to 10 carbon atoms, but mainly contains alkylbenzenes, polyalkylbenzenes, naphthalene, and many other aromatic hydrocarbons. Although it is obtained in large quantities along with BTX fraction, there was no effective way to use it. In the present invention, the pyrolysis oil fraction of (A) is added to the pyrolysis oil fraction of (B).
(a) thermal decomposition by-product oil fraction, (b) reformed oil fraction, and (c) aromatic fraction are mixed and subjected to acid catalyst treatment. The fractions (a) to (c) can be appropriately mixed and used as the fraction (B). The mixing ratio of both is (A) pyrolysis oil fraction 20-95
The fraction (B) is 80 to 5% by weight. When the obtained reaction product is used as an electrical insulating oil, a more preferable mixing ratio is 70 to 90% by weight of the fraction (A) and the fraction of B, since it provides excellent low-temperature properties.
It is 30-10% by weight. As the acid catalyst, 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 SnCl4 , 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 aerated acid catalyst is added to the fraction in an amount of 0.2 to 20% by weight in a batch system, preferably 1 to 10% by weight, and the LHSV is 0.1 to 20, preferably 0.5 to 10 in a flow system. Process with. Reaction temperature is 30~
The temperature is 300°C, preferably 50-250°C. 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 to complete the reaction, and it can usually be selected within the range of 2 to 24 hours. The reaction pressure may be any pressure necessary to maintain the liquid phase. In the present invention, the above acid catalyst treatment is carried out at a boiling point.
Carry out so that a reaction product with a temperature of 315°C or higher is obtained. The reaction product is mainly a reaction product of aliphatic olefins, and is mainly composed of oligomers of aliphatic olefins and alkylates of aliphatic olefins and aromatic hydrocarbons. A reaction product with a boiling point lower than 315°C has a low flash point, etc., and is not valuable as an insulating oil, and there is no point in acid catalyst treatment, so it is not preferred. In the present invention, as mentioned above, a fraction of a specific composition from a specific source is used as a raw material and is subjected to a specific treatment, so that virtually no high molecular weight compounds that adversely affect various physical properties are generated. The reaction product has a relatively low viscosity. Therefore, depending on the application, it is possible to use it as an insulating oil by simply separating the unreacted fraction (raw material fraction), for example, by distillation, without further separating the heavy fraction. Of course, the product can be divided into suitable boiling range fractions if desired. Although the unsaturated content of the pyrolysis oil fraction is reduced by the above treatment, for example, the bromine number is reduced, the reaction product contains oligomers of aliphatic olefins as described above, so it is preferable to By performing catalytic hydrogenation treatment, unsaturation is reduced or eliminated. In addition, the catalytic hydrogenation treatment can also be performed on the separated reaction product or a fraction containing a large amount of the reaction product, or the pyrolysis oil fraction itself that has been subjected to the acid catalyst treatment. can. 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, Ni-W, etc. 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 , a hydrogen/oil molar ratio of 0.5 to 20, and a LHSV of 0.1 to 10. This hydrogenation treatment is carried out under conditions in which hydrogenation of the aromatic hydrocarbons does not substantially occur. After the catalytic hydrogenation treatment, reaction products and, if necessary, gas components are separated by appropriate means such as distillation. Of course, the hydrogenation reaction product may be further separated into appropriate fractions. The hydrogenation reaction product thus obtained has a boiling point of 315°C or higher, a viscosity of 25 cst or lower at 75°C, a pour point of -40°C or lower, and a flash point of 140°C or higher. Although its composition varies depending on the boiling point range of the raw materials, mixing ratio, etc., it contains almost no normal paraffins, and contains isoparaffins, aromatic hydrocarbons containing alkyl-substituted monocycles or complex rings, etc. It consists of 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 and the pyrolysis by-product oil of petroleum light oil, or the high boiling point fraction (bp 150 to 250°C) in catalytically reformed gasoline, is available for use. That is, the industrial value is low, and the industrial value is high because it is possible to effectively utilize a large amount of surplus heavy residual oil. At the same time, products with high industrial value can be obtained by using high-boiling fractions with low industrial value that are by-produced during the production of high value-added benzene, toluene, xylene, etc. (2) Since the raw material is a fraction of a specific structure of a specific raw material, and a specific treatment is carried out, virtually no high-molecular weight substances that would adversely affect physical properties are produced, and only relatively low-viscosity substances are produced. can get. Therefore, if possible, it has the advantage that it can be used as an inexpensive electrical insulating oil by simply distilling the unreacted oil fraction. Furthermore, even though pyrolysis oil from heavy residual oil is used as a raw material, electrical insulating oil with low unsaturated content, metal content, and sulfur content can be obtained. Next, the present invention will be explained in detail with reference to Examples. Example 1 Delayed coking equipment for coking vacuum distillation residue oil with properties shown in Table 1 obtained from Minas crude oil (decomposition temperature 496°C, residence time 24 hours, decomposition pressure 4
Kg/cm 2 ) Pyrolysis oil was obtained together with gas and coke at the yield shown in Table 2. Of these, the boiling point is 160~
The fraction at 260°C is designated as fraction A, and its composition is shown in Table 3.
【表】【table】
【表】【table】
【表】
芳香族オレフイン分 −
[Table] Aromatic olefin content −
Claims (1)
分解して得られた熱分解油留分であつて、沸点
120〜290℃の範囲にある炭化水素を主成分と
し、かつ脂肪族オレフインを含む熱分解油留分
20〜95重量%と、 (B) (a) 石油系軽質油を温度750〜850℃で熱分解
し、次いで不飽和分を減少させる処理を施し
て得られた熱分解副生油留分、 (b) 沸点50〜250℃の石油系軽質油を接触改質
し、次いで必要に応じて不飽和分を減少す処
理を施して得られた改質油留分、および (c) 上記(a)の熱分解副生油および/または(b)の
改質油留分を原料として、分離取得された芳
香族炭化水素を主とする芳香族留分からなる
群から選ばれる1種または2種以上の沸点
150〜250℃の留分80〜5重量%とを、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315℃以上の反応生成物
を得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 (A) 石油系重質残油を400〜600℃の温度で熱
分解して得られた熱分解油留分であつて、沸点
120〜290℃の範囲にある炭化水素を主成分と
し、かつ脂肪族オレフインを含む熱分解油留分
20〜95重量%と、 (B) (a) 石油系軽質油を温度750〜850℃で熱分解
し、次いで不飽和分を減少させる処理を施し
て得られた熱分解副生油留分、 (b) 沸点50〜250℃の石油系軽質油を接触改質
し、次いで必要に応じて不飽和分を減少させ
る処理を施して得られた改質油留分、および (c) 上記(a)の熱分解副生油および/または(b)の
改質油留分を原料として、分離取得された芳
香族炭化水素を主とする芳香族留分からなる
群から選ばれる1種または2種以上の沸点
150〜250℃の留分80〜5重量%とを、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315℃以上の反応生成物
を生成せしめ、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下で接触水素添
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プロセスで
ある特許請求の範囲第3項記載の方法。[Scope of Claims] 1 (A) A pyrolysis oil fraction obtained by thermally decomposing petroleum heavy residual oil at a temperature of 400 to 600°C, which has a boiling point
Pyrolysis oil fraction whose main component is hydrocarbons in the range of 120 to 290℃ and also contains aliphatic olefins.
(B) (a) A thermal decomposition by-product oil fraction obtained by thermally decomposing petroleum light oil at a temperature of 750 to 850°C and then performing a treatment to reduce unsaturated content, (b) A reformed oil fraction obtained by catalytically reforming light petroleum oil with a boiling point of 50 to 250°C, and then optionally subjected to treatment to reduce unsaturated content, and (c) the above (a) One or more types selected from the group consisting of aromatic fractions mainly consisting of aromatic hydrocarbons separated and obtained using the thermal decomposition byproduct oil of (b) and/or the reformed oil fraction of (b) as raw materials. boiling point of
A reaction product having a boiling point of 315°C or higher is obtained by treating 80 to 5% by weight of a fraction of 150 to 250°C in the liquid phase in the presence of an acid catalyst at a reaction temperature of 30 to 330°C. Manufacturing method of electrical insulating oil. 2. The method of claim 1, wherein the pyrolysis process is a coking process. 3 (A) A pyrolyzed oil fraction obtained by thermally decomposing petroleum heavy residual oil at a temperature of 400 to 600°C, which has a boiling point
Pyrolysis oil fraction whose main component is hydrocarbons in the range of 120 to 290℃ and also contains aliphatic olefins.
(B) (a) A thermal decomposition by-product oil fraction obtained by thermally decomposing petroleum light oil at a temperature of 750 to 850°C and then performing a treatment to reduce unsaturated content, (b) A reformed oil fraction obtained by catalytically reforming petroleum-based light oil with a boiling point of 50 to 250°C, and then optionally subjected to treatment to reduce unsaturation, and (c) the above (a) One or more types selected from the group consisting of aromatic fractions mainly consisting of aromatic hydrocarbons separated and obtained using the thermal decomposition byproduct oil of (b) and/or the reformed oil fraction of (b) as raw materials. boiling point of
A reaction product with a boiling point of 315°C or higher is produced by treating 80-5% by weight of a fraction of 150-250°C in the liquid phase in the presence of an acid catalyst at a reaction temperature of 30-330°C, and then aromatic A method for producing electrical insulating oil, characterized by carrying out catalytic hydrogenation treatment under conditions in which nuclear hydrogenation of hydrocarbons does not substantially occur. 4. The method of claim 3, wherein the pyrolysis process is a coking process.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2185084A JPS60167205A (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 |
---|---|---|---|
JP2185084A JPS60167205A (en) | 1984-02-10 | 1984-02-10 | Electrically insulating oil |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS60167205A JPS60167205A (en) | 1985-08-30 |
JPH0438083B2 true JPH0438083B2 (en) | 1992-06-23 |
Family
ID=12066574
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2185084A Granted JPS60167205A (en) | 1984-02-10 | 1984-02-10 | Electrically insulating oil |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS60167205A (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 JP2185084A patent/JPS60167205A/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 |
---|---|
JPS60167205A (en) | 1985-08-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6904964B2 (en) | Processes and equipment with improved product yields for converting crude oil to petrochemicals | |
CN109593557B (en) | Process and installation for converting crude oil into petrochemicals with improved propylene yield | |
US9193921B2 (en) | Hydrocracking process for a hydrocarbon stream | |
WO2008043066A2 (en) | Process to produce middle distillate | |
EP0090437B1 (en) | Process for the production of hydrocarbon oil distillates | |
US3786107A (en) | Method of producing alkyl aromatics | |
JP4417105B2 (en) | Multistage process for sulfur removal from transportation fuel blending components | |
US11473023B2 (en) | Hydrocarbon pyrolysis processes | |
CN101747129A (en) | Method for producing light olefins through catalytic conversion | |
JPH0462772B2 (en) | ||
US9162943B2 (en) | Method of converting a coal to chemicals | |
US4755275A (en) | Electrical insulating oil | |
JP4417104B2 (en) | Multistage process for sulfur removal from transportation fuel blending components | |
US20150136652A1 (en) | Process for hydrotreating a coal tar stream | |
IL35865A (en) | High octane gasoline production | |
JPH0438083B2 (en) | ||
CA1232562A (en) | Method of processing thermal-cracked oil distillates | |
US4735703A (en) | Method of increasing the concentration of straight chain paraffin material | |
JPS5950197B2 (en) | Processing method for pyrolysis byproduct oil | |
JPH0552353B2 (en) | ||
EP0082551B1 (en) | Process for the production of hydrocarbon oil distillates | |
US20150141723A1 (en) | Process for hydrotreating a coal tar stream | |
JPH0552352B2 (en) | ||
JPH0434245B2 (en) | ||
JPH0438084B2 (en) |