JP3604414B2 - Hydrocracking method using in-situ prepared colloidal catalyst - Google Patents

Description

以下の表１は実験操作の間に用いた希釈剤の組成（重量％）を示す。
【００６３】
縮合ジシクロパラフィン類及びベンゼンシクロパラフィン類の相対含有量に従って、希釈剤Ｂは最高の水素供与能力を有し、かつ希釈剤Ｃは最低の能力を有することが注目される。
【００６４】
【表１】

実施例Ｉ
この実施例では異なる希釈剤の影響について説明する。オートクレーブには、１０９ｇのビチューメンと２２０ｇの希釈剤Ａ、Ｂ又はＣを入れる。０．５５ＭＰａの窒素過剰圧力を加え、内容物を４３０℃で１０５分間熱的にクラッキングした。
【００６５】
試験の結果は表２に示す。反応器を開き、実験ＣＦ−３０、ＣＦ−９及びＣＦ−３１のバッフル板上に析出したコークスを図７、８及び９にそれぞれ示す。
【００６６】
実験ＣＦ−３１では実験ＣＦ−９より多くのコークスが生成したが、このコークスはバッフル板及び反応器表面から最も容易に除去されたことが注目される。さらに、実験ＣＦ−３１はＣＦ−３０の約２倍多いコークスを生成したがこのコークスは最も容易に除去された。実験ＣＦ−３１の反応器及びバッフル板の表面は最も汚れていなかった。
【００６７】
３つの実験からのコークスは顕微鏡で検査し、結果を図１０に示す。凝集物濃度（異方性であった）が比較的高い場合（実験ＣＦ−３１）、コークスの析出及び粘着は、希釈剤Ｃが最も低い水素供与能力を有するにもかかわらず、最も弱いものであった。
【００６８】
【表２】

実施例ＩＩ
この実施例では水素過剰圧力の効果について説明する。
【００６９】
実験条件及び結果を表３に示す。実験ＣＦ−Ａ３は実験ＣＦ−９と比較する。
【００７０】
図１１は実験ＣＦ−Ａ３のバッフル板の上に析出したコークスを示す。実験ＣＦ−９（図８）と比較して、実験ＣＦ−Ａ３のコークス収率及び析出は少なかった。
【００７１】
図１２は実験ＣＦ−Ａ３から得たコークスの顕微鏡検査の結果を示す。実験ＣＦ−９の図１０に示す結果と比較するもので、結果は同様である。
【００７２】
両実験において、コークス成分の８０％以上が異方性タイプのものであった。実験ＣＦ−Ａ３凝集濃度は実験ＣＦ−９のそれより著しく大きいものではなかった。
【００７３】
この実施例は、水素のみが豊富であると、コークス前駆体の粘着性を中和できないか、又は選択的にコークス組成を変性できないことを教示する。
【００７４】
【表３】

実施例ＩＩＩ
この実施例は、多くの凝集物を含むコークスは粘着性でないことを示す。
【００７５】
実験ＣＦ−Ａ３と実験ＦＥ−１の結果及び条件は表４示す。
【００７６】
図１３は実験ＦＥ−１のバッフル板上にコークスの析出がないことを示す。実験ＣＦ−Ａ３（図１１）と比べ、実験ＦＥ−１のコークス収率及び析出は少ない。
【００７７】
実験ＦＥ−１からのコークスは、反応器の底部にゆるく沈澱した微細な粒子であると観察された。
【００７８】
【表４】

図１２は実験ＣＦ−Ａ３と実験ＦＥ−１から得たコークスの顕微鏡試験の結果を示す。これらの結果は非常に異なるものである。実験ＦＥ−１からのコークスは８０％以上が等方性凝集物である。
【００７９】
実験ＦＥ−１の図１４と１５は、固体粒子は全て互いに弱く化合していることを示した。コークス組成は成分の９７％以上が異方性であることを示した。（図１２参照）。等方性凝集物はコークス組成の８０％であった。。
実験ＦＥ−１のこのデータは、コークス前駆体の粘着性は高度に分散された鉄化合物により効率的に中和されたことを示した。等方性球体が濃縮されたとき（図１５参照）、等方性凝集物は、この球体の基本等方性粒子への合体を効率的に防止した。
【００８０】
鉄スルフィドとして存在する添加剤はコークス重量の約１／３に達するがそれ程明白ではないことも注目される。
【００８１】
実施例ＩＶ
この実施例は、希釈剤の選択が望ましいことをさらに示す。
【００８２】
実験ＣＦ−３８は米国特許第４，４５５，２１８（ダイモック（Ｄｉｍｏｃｋ）ら）の教示に従って行った。実験条件は、実験ＦＥ−１について表４に示したものと同一である。全アタバスカビチューメンがアタバスカＶＴＢの代わりに用いられ、かつ希釈剤は添加しなかった。全ビチューメンは５０４℃以上の温度で沸騰する炭化水素を約６０重量％含有した。ビチューメン中の５０４℃^＋ 含有量の等量基準で０．５％（金属）の鉄ペンタカルボニルを添加した。
【００８３】
コークス収率は７．９％（５０４℃^＋ 基準）であり、このコークスは反応器及びバッフル板の表面に非常に強力に粘着した。図１６はバッフル板上に析出したコークスを示す。
【００８４】
実施例Ｖ
この実施例は、反応流体からの高度に揮発性成分の連続的除去の速度の影響を示す。
【００８５】
１リットルのオートクレーブに反応器にＮ_２ 又はＨ_２ を散布する挿入管、生成ガスの連続流出が可能な出口及び揮発生成物をガス流から分析のためのサンプルバックにガスが捕集される前に除去するためのコールドトラップ冷却器を備えた。実験は前記反応器中で４３０℃で１０５分間、５５０ｋＰａの圧力下、ガス流なしで、及び反応器内及び外の連続的ガス流ありで、行った。各実験では、１１０ｇのアタバスカ５０４℃^＋ 真空塔残油（ＶＴＢ）と２２０ｇの希釈剤を用いた。以下の表５は反応条件と実験結果を示す。
【００８６】
【表５】

【表６】

図１７は窒素の流速の関数としてのコークス生成量を示す。希釈剤Ａ及びＢについて示すように、コークス生成量は窒素流速が増加すると減少した。窒素の高流速においては、希釈剤Ｂ（最良の水素供与体溶媒）を用いた実験におけるコークス生成量は、希釈剤Ｂ（最悪の水素供与体溶媒）を用いた実験のそれとは非常に異なってはいなかった。
【００８７】
表５において、少ないコークス生成量を与える条件については、排出ガスから回収される凝縮物の量は最も多かったことが注目される。これは希釈剤Ａ及びＢの両者について言えることである。
【００８８】
表６は実験５からの凝縮物の模擬蒸留の結果を示す。この凝縮物の約９０％は２２０℃以下の温度で沸騰する。
【００８９】
この実施例はコークス生成は、低沸点生成物が反応流体から連続的に除去（ストリップ）されると減少することを示す。さらに、コークス生成は低沸点生成物が希釈剤から除去すると減少することも示す。
【００９０】
これらの観察は、反応流体から別の液相としてアスファルテン類分離を有するモデルに一致する。ペンタンをビチューメンに添加して室温で固体アスファルテンを得る一般の実験と類似して、そのような高温で行われる実験は、分離液相としてアスファルテンが得られると予期される。さらに、この分離液相は熱的に分解してコークスを生成するアスファルテン類に富むであろうと予想される。
【００９１】
この相分離は、模式的に図１８に示す。この図の３つの成分は、それぞれラベルされたアスファルテンの芳香族と脂肪族と脂環式の５０４℃^＋ 、２２０〜５０４℃及び２２０℃の沸点を有する留分をそれぞれ示す。矢印は、実施例ＩＶで起こったであろう全ビチューメンの組成の発生を示す。
【００９２】
実施例ＶＩ
本実施例は、反応流体からの高度に揮発性の成分を連続的に除去するための水素の使用の効果を示す。
【００９３】
予熱器、２リットル撹拌反応器及び生成物捕集システムからなる連続フローシステムを用いた。バッフル板及び攪拌機は前の実施例のものと類似のものである。アタバスカＶＴＢ、希釈剤Ａ及び予熱水素の混合物は、予熱器を介して撹拌反応器の底部にポンプで流し込まれた。生成物は反応器の高さの６０％の所にその入口がセットされたディップ管を介して除去された。
【００９４】
実験条件及び結果は、実験７、８及び９については表７に示す。各実験において、水素流速は１２ｓｌｐｍであった。実験７では、液空間速度は実験８及び実験９のそれの２倍である。反応流体の温度は実験８のそれの２０℃高い。
【００９５】
注目すべきは、ハイドロクラッキングの厳しさは実験７から８、さらに９になるほど増すにもかかわらず、実験８における生成コークス量は実験７のそれより少なかったこと及び実験９ではほとんどコークスが生成しなかったことである。
【００９６】
そのような結果は、反応流体の高度に揮発性の留分が、条件が実験７から８、さらには９に変化したときに効率を増して除去されると考えると予期される。実験９では、反応器を生成物捕集器に繋ぐパイプが実験終了時には、詰まった。
【００９７】
実験１０では、２つの１リットル反応器を並べて配置し、反応器の高さの５０％及び７０％の位置にディップ管の入口を設置した。条件及び結果を表７に示す。
【００９８】
【表７】

転化率は実験８と同様であった。このことは、異なる液空間速度と異なる反応器の数を与えることを予想させる。しかし、実験１０の水素流速が速いにもかかわらず、実験１０で生成したコークス量は、実験８での生成量より多かった。
【００９９】
この実施例は、水素流及び反応温度は、反応流体から低沸点生成物を除去（ストリップ）して、生成するコークス量を減らすのに上手に用いることができるであろうことを教示する。さらに、一連の１つ以上のハイドロクラッキング反応器については、１つの反応器の有する配置は、少量のコークスを生成するだけであることを教示する。さらに、多数のハイドロクラッキング反応器を並べて配置すると、１つの反応器から次の反応器に移る際、流体から揮発炭化水素が除去されると、コークス生成量は少なくなることを教示する。
【０１００】
実施例ＶＩＩ
本実施例は、反応器の配置、反応の厳しさ、揮発成分のストリッピング及び添加剤の上手な使用によってＶＴＢの蒸留生成物への高い転化率が、許容できるコークス生成と反応器の最少限の汚れで、得られることを示す。
【０１０１】
実施例ＶＩの実験７、８及び９の連続フローシステムを用いた。添加剤は鉄ペンタカルボニルであった。実験１１と１２の条件と結果とを表８に示す。
【０１０２】
実験１２の条件は実験１１のそれより大変厳しいものであった。にもかかわらず、反応器、パイプ及び捕集容器の全ての表面は、コークスによる汚れがなく、かつ生成したコークスは、生成物捕集容器中に沈澱した微細な砕けやすい物であった。
【０１０３】
実験１２の生成コークスの顕微鏡試験結果は、表９に示す。コークスの７４％が凝集物の形態であった。コークスの２３％は等方性球体の形態であったが、これらの球体は、凝集物のマトリックス中に隔離され捕獲されていた。
【０１０４】
この実施例は生成コークスの大半が凝集物である場合、最少限の反応器の汚れで高い転化率が得られるであろうことを教示する。
【０１０５】
【表８】

実験１２においてＨ_２ の流れが増えなかったら、転化率の１４％の増加は、記録された量より相当に高いコークス収率によって、得られたものであると予想したであろうことに注意すべきである。
【０１０６】
【表９】

実施例ＶＩＩＩ
本実施例では、種々の添加剤及び種々の金属化合物を比較した。
【０１０７】
以下の添加剤を用いた一連のテストでは、それらのコークス生成及び析出の防止における相当効率の比較を行った。
【０１０８】
○ 微細アルベルタ（Ａｌｂｅｒｔａ） 木炭
○ 油溶性ニッケルナフタネート
○ 油溶性コバルトナフタネート、及び
○ 油溶性モリブデンナフタネート
鉄ペンタカルボニルを比較の基準として用いた。
【０１０９】
全てのテストは、以下の一般的反応条件で行った。
【０１１０】
０．５重量％（金属、真空塔残油基準）添加剤、アタバスカ真空塔残油（３３．３％）、希釈剤（６６．７％）、６．８Ｍｐａ初期水素圧力、８００ｒｐｍ撹拌速度、４３０℃、及び１０５分の反応時間。アルベルタ木炭の場合、添加量は、真空塔残油の４％に相当する量とした。
【０１１１】
図１９の圧力曲線及び図２０の水素消費結果は、水素消費について以下の観測順を示した。
【０１１２】
モリブデン添加剤（ＣＦ−４０）６８％
ニッケル 添加剤（ＣＦ−４１）３９％
コバルト 添加剤（ＣＦ−４１）２７％
鉄 添加剤（ＦＥ−１） ２６％
及び木炭 （ＣＦ−４３）２１％
表１０の生成物分散は以下の添加剤順序を示した。
【０１１３】
○ 真空塔残油転化率
モリブデン＞鉄＞木炭＞ニッケル＞コバルト
○ Ｃ_５ −５０４℃の選択率
ニッケル＞鉄＞コバルト＞モリブデン＞木炭
○ コークス生成
ニッケル＜コバルト＜木炭＜鉄＜モリブデン
図２１は、コークス前駆体を転化して非析出等方性凝集物コークス粒子を形成する際の種々の添加剤の有効性を示す。モリブデン含有添加剤を用いた実験は最も多い量の水素を消費したが、コークスの９０％以上は基本等方性粒子であった。図２２中、実験ＣＦ−４０からのコークスは基本等方性粒子の連続シートとして表れていた。実験ＣＦ−４０からのコークスは鉄添加剤を用いた実験ＦＥ−１からのコークスより明らかに密に充填されていた（図１４〜１５）。
【０１１４】
先に指示したように、反応器壁へのコークスの析出を防止するためには、添加剤はコークス前駆体球体を等方性凝集物に選択的に変換しなければならない。実験ＣＦ−４０からのコークス中に等方性凝集物が含まれていないことは、反応器バッフル板上への粘着性コークスの析出（図２３）の説明を示唆する。一方、鉄ペンタカルボニルを用いた実験での反応器バッフル板（図１３）には、粘着性コークスが全くなかった。
【０１１５】
この実施例は、添加剤を適当に選ぶことにより、コークス生成を防止でき、かつ適当な希釈剤を用いると粘着性コークスの析出を防止できるであろうことを教示する。そのような添加剤は、等方性凝集物の形態のコークス留分を最少限にする。鉄又はコバルト又はニッケル又はこれらの組合せを含む油溶性添加剤が好ましい。
【０１１６】
【表１０】

実施例ＩＸ〜ＸＩＩ
これらの実施例は全体として以下の主張を支持する。
【０１１７】
１． 添加剤分散は分解温度以下で行う必要があり、かつアスファルテン類中に添加剤を均一に分散するために温和な加熱温度における長時間の混合を必要とする。
【０１１８】
２． 添加剤の分解を引き起こす消化は混合条件下で行う必要がある。さらに、
３． 前記添加剤選択、溶媒の好ましい使用、分散及び消化工程、並びにハイドロクラッキングの間のストリッピング及び混合の組合せは一緒になって、粘着性コークス形成のほとんどない高い５２５℃^＋ 転化率を可能にするコロイド状触媒粒子を生成する。
【０１１９】
換言すると、もし添加剤が、相当な分解が起きる前に分子スケールで十分に分散されていないと、おそらく、相対的に大きい、非コロイド状の、ミクロン以上のサイズの触媒粒子が生成し、粘着性コークスの生成があり、かつ転化率も低いであろう。同様に、もし添加剤の分解が分散を保つための混合なしに起こったら、非コロイド状触媒が生成し、その結果、コークスが生成し、転化率も低いであろう。
【０１２０】
実施例ＩＸ
この実施例（実験ＴＲＵ１０１とＢ３−１に関する）は、添加剤の分解温度より十分低い温度である加熱温度において長時間添加剤を混合することにより適切に分散することが望ましいことを示す。他の点では、混合物が次いでハイドロクラッキング温度に急激に加熱された場合、猛烈な汚れが、ヒーター内又は反応器入口で起こり、閉塞が生じ、この閉塞は、循環系内の圧力の動揺によって特徴付けられる。
【０１２１】
図２５には、これらのテストに用いた系を示す。図２６〜２８は図２５上に示された点で実験ＴＲＵ１０１の間に得られた圧力記録を示す。
【０１２２】
混合及び分散容器（「ミキサー」）にポンプと帰り管とを設け、原料が循環及び混合できるようにした。供給源からの水素は、ミキサーからの生成物を取り出す管に加えた。混合物は加熱器を通して温度をハイドロクラッキング温度に上げた。加熱器生成物に次いでハイドロクラッキング反応器中に導入した。反応器生成物は、ホットセパレーターを通してピッチを生成した。
【０１２３】
以下に最初の実験（ＴＲＵ１０１）に関する条件を示す。
【０１２４】

ミキサーは初めスタートから１７．１時間に１３５℃で操作した。ミキサー温度は次いで１５０℃（添加剤の分解温度以下である）に昇温した。スタートから２５．９時間後、最初の圧力振動がＰＴ４５５で観測され、ホットセパレーターへの入口の下流で弱い閉塞が起こったことを示唆した。スタートから８５．３時間後にＰＴ３２０で１６．３Ｍｐａへの圧力振動が観測され、ＰＴ３２０とＰＴ３４０の間で軽微な閉塞が起きたことを示唆した。閉塞を開放するとＤＰ４５０で圧力振動が観測され、該閉塞が反応器及びホットセパレーターへの下流を通って押し出されたことが示唆された。スタートから９９時間後、ＰＴ４００での圧力が１５．２Ｍｐａに振動し、反応器への入口で閉塞が形成されたことを示唆した。スタートから１０８．９時間後、強い閉塞が反応器入口で形成されたために、ＰＴ４００及び上流での圧力が２１．６Ｍｐａに飛び上がった。
【０１２５】
これらの結果は、以下の観測結果を与える。
【０１２６】
閉塞は、分散が１３５℃で行われたときには問題ではなかったが、１５０℃では問題となった。さらに
添加剤の分解は、非混合条件下では加熱器中又はその周辺で起こった。このことはパイプを閉塞する大きな鉄粒子の形成を起こさせる。
【０１２７】
同じ系を実験Ｂ３−１にも用いた。この実験に関する条件は以下のとおりである。
【０１２８】

実験Ｂ３−１は２２５時間続けた。実験ＴＲＵ１０１と比べて以下の違いがあった。
【０１２９】
○ 分散温度が低かった。
【０１３０】
○ 添加剤濃度が少なからず減少した。
【０１３１】
○ 反応器温度がやや低かった。
【０１３２】
実験Ｂ３−１の圧力記録を図２９〜３０に示す。
【０１３３】
順調で閉塞のない操作が実質的に全てのテスト中観測された。約１６０時間後にセパレーターの上流の圧力が、閉塞が生じ破れたことで、わずかに約１９．０Ｍｐａに振動した。ユニットの閉塞及び汚れは、実験Ｂ３−１では実験ＴＲＵ１０１より顕著に少なかった。
【０１３４】
この実験は、分解温度により相当に低い温度での分散及びハイドロクラッキング温度への急速な加熱が望ましいことを示す。
【０１３５】
実施例Ｘ
本実施例は、油中に添加剤を高濃度で添加した場合、及び分散を分解温度を超えた高い温度で実施した場合、良い結果が得られないことをを示す。
【０１３６】
本テストでは、分散及び分解は第一の部位で一段落で行い、混合生成物はハイドロクラッキングのため別の部位に移送された。移送を容易にするために濃度（Ｆｅ４重量％）は第一の部位で形成された。用いた２つの循環系を図３１及び３２に示す。
【０１３７】
実験の条件は図面と共に示されている。
【０１３８】
この系におけるいくつかの実験結果は以下のとおりである。
【０１３９】
【表１１】

生成ピッチからの固体の電子顕微鏡分析によれば、ＦｅＳｘ粒子は典型的には５μｍの直径を有していた。
【０１４０】
ピッチ転化率（５７〜６８％）は比較的悪く、かつ反応器循環系中にコークスが生成していた。
【０１４１】
実施例ＸＩ
本実施例は、実施例Ｘの追加であり、かつビチューメンと添加剤とが、予め低温で混合されることなしに分解温度で消化のみさせた場合、混合しながら消化させても良い結果は得られないことを示す。
【０１４２】
図３３はパイロット循環系であり、本実験ではいくつかの条件を用いた。図３４はこの実験における圧力記録を示す。
【０１４３】
本テストにおいての条件は以下のとおりである。
【０１４４】
○ 供給： アタバスカビチューメン、組成：４５％２２０〜５２４℃、５５％５２５℃^＋
○ 供給速度： ２．８１５ｋｇ／ｈｒ
○ 添加剤： 軽油中に３３重量％の鉄ペンタカルボニル
○ 添加速度： ３２．９ｍｌ／ｈｒ
○ 添加剤濃度：５２５℃^＋ 留分に対して５０００ｐｐｍ
○ 水素： ３４標準リットル／分（４０００ＳＣＦ／ＢＢＬ）
○ 消化温度： ２５０℃
○ 反応器条件：４５０℃、１０．２Ｍｐａ
反応器を横断する圧力降下は、実験の間に徐々に増加し、３３時間後に急激に増加した。循環系は、ＰＴ２３Ａにおける記録圧力が増大して３６時間後に操作不能になった。
【０１４５】
生成ピッチからろ過した物質の試験によれば、鉄スルフィド粒子径は１〜２μであった。
【０１４６】
実施例ＸＩＩ
本実施例は、適切な分散が添加剤分解温度より十分に低い温度である穏やかな、即ち温和な温度で行われ、かつ分解が混合を伴って行われた場合、良好な転化率とコークスの減少結果が得られることを示す。
【０１４７】
図３５は本実験に用いた循環系及び条件を示す。図３６は実験からの種々の記録を示す。
【０１４８】
本テストでは、ビチューメンと鉄ペンタカルボニルとを羽根車付第１の容器中で約１００℃の温度で約３０分間混合して添加剤を分散し、次いで羽根車付第２の容器中で約２５０℃の温度で約１時間混合して、分散しながら分解した。
【０１４９】
次の表１２は別の条件及び実験結果を示す。
【０１５０】
【表１２】

最初の１００時間の操作は順調でかつ閉塞も見られなかった。その時点でポンプが故障した。修理の後、反応器を横断する圧力降下に少し動揺が記録されたが、循環系の操作は全く順調であった。ピッチ転化率は、約３００時間の実験の間に、８４％から９２％に徐々に増加した。
【０１５１】
試験の結果、コロイド状鉄スルフィド粒子の形態のピッチ中に存在すべき添加剤の鉄が示された。
【０１５２】
実施例ＸＩＩＩ
本実施例は、異なる温度においてモリブデンナフタネート（「Ｍｏ−ｎａｐｈ」）とモリブデンエチルヘキサノエート（「Ｍｏ−ＨＥＸ」）の分解範囲を示すデータを提供する。
【０１５３】
詳しくは、Ｍｏ−ｎａｐｈ又はＭｏ−ＨＥＸのいずれかを含有するビチューメンサンプルの赤外スペクトルを１３０℃、２００℃及び３００℃の温度において一定時間測定した。以下の表に、これらの触媒前駆体の各々の分解パーセントを与えられた時間で消失したそれぞれのスペクトル成分の関数（％）として表した。
【０１５４】
【表１３】

実施例ＸＩＶ
本実施例は、本発明の方法により生成される触媒粒子はコロイドサイズであることを示す。
【０１５５】
実験ＣＦＥ−１で生成したピッチのサンプルをＸ線回折及びモスバウアー（Ｍｏｓｓ ｂａｕｅｒ）分光計で検査した。
【０１５６】
Ｘ線回折試験によりＦｅＳ_２ の存在が明らかになった。
【０１５７】
モスバウアー分析のスペクトルを図２４に示す。確認データを以下の表１４に記載する。スペクトルにおいてそれぞれのピークの幅が重要である。そのような幅は、典型的には直径が１０ナノメーター以下の非常に細かいコロイド状粒子を示す。
【０１５８】
本テストの前、化学分析ではピッチ中に２０重量％以上の鉄スルフィドを示してはいたが、本発明に従って行った実験から得られたピッチのサンプルの顕微鏡試験は、鉄スルフィド粒子についての証拠はなかった。この証拠は、触媒粒子は顕微鏡サイズ以下であることを示す。
【０１５９】
【表１４】

実施例ＸＶ〜ＸＩＸ
これらの実施例は、添加剤又は触媒前駆体としてモリブデンナフタネートを用いた実験に基づく。
【０１６０】
実験ではビチューメンからの真空塔残油を原料として用いた。原料の性質と組成は以下のとおりである。
【０１６１】
【表１５】

報告した実験で用いた循環系は、図２５のものである。モリブデンナフタネートを、モリブデン３００ｐｐｍとなるように原料に添加した。原料は、撹拌し、実験前に２００℃で３時間ループ管をポンプで循環された。テストは１２〜１５時間行った。
【０１６２】
実施例ＸＶ
本実施例は、固型コークスの生成が最少で高いアスファルテン転化率が、添加剤としてモリブデンナフタネートを用いて本発明を実施したときに得られることを示す。
【０１６３】
コールド・レーク（Ｃｏｌｄ Ｌａｋｅ） 真空残油のアスファルテンに富んだ供給原料（ＩＢＰが４３０℃以上）を０．０１ｍ^３ のサージングタンクに充填した。
【０１６４】
モリブデンナフタネートをモリブデンが３００ｐｐｍになるように、攪拌器と循環ポンプを備えた上記タンクに添加し、２００℃で窒素雰囲気下で混合して均一混合物を形成した。この混合物は、プロセスヒーターを介して反応器中にポンプで導入した。温度は、プロセスヒーター中で４５５℃に上昇させた。水素は、プロセスヒーターの入口で混合物に添加した。水素は、１０，０００〜１２，０００ＳＣＦ／ＢＢＬの速度で、かつ２０００ｐｓｉｇの圧力で供給した。プロセスヒーターは、ハイドロクラッキング温度のスズに浸漬した内径（Ｉ．Ｄ．）２．９ｍｍ、長さ６１００ｍｍものであった。
【０１６５】
ハイドロクラッキング反応器の容量は６６９ｃｍ^３ であった。それは、内径（Ｉ．Ｄ．）２５ｍｍ、高さ１３７０ｍｍのステンレス鋼製円筒であった。
【０１６６】
反応器操作の条件は以下のとおりである。
【０１６７】
Ｈ_２ ／液体の容量流れ＝１０，０００ＳＣＦ／ＢＢＬ
液体ペクレットＮｏ．＝約０．２５
ガスペクレットＮｏ．＝約６
（これらのペクレットＮｏ．はＸｅ^１３３ 及びＩ^１３１ を用いたトレーサー試験から決定した。）
ＬＨＳＶは０．４〜１．０ｈ^−１であった。反応器が定常操作条件に達するのに通常１０〜１２時間を要した。ハイドロクラッキングは４５５℃の温度かつ２０００ｐｓｉｇの圧力で行った。ガスと液体の混合物を含む反応器流出液は、ガスと液体とを分離するホットセパレーターに送られた。
【０１６８】
表１６は本方法の典型的結果を示す。
【０１６９】
【表１６】

上記ハイドロクラッキングテストは、表１５に記載されたコールド・レーク真空残油について行われ、前駆体濃度は、原料基準で３００ｐｐｍのＭｏであった。各テストの後、実験系の全てのユニットは開けられ、検査されてコークス及び他の汚れのないことが確認された。
【０１７０】
Ｍｏを用いた実験は原料とてＶＴＢを用いたにもかかわらず溶媒なしで良好に行えたことは注目すべきである。
【０１７１】
実施例ＸＶＩ
本実施例は、実施例ＸＶの触媒がコロイド状であったことを示す。
【０１７２】
ハイドロクラッキング残油をメチレンクロライドに分散し、混合物をゲル透過カラムに注入した。モリブデン含有成分は、ポリスチレンにより校正したこのゲル透過カラムに関して４００から３０００の明白な分子量範囲を有することがわかった。この範囲は、０．００２ミクロン以上で０．０１ミクロン以下の直径のコロイド状粒子に相当する。
【０１７３】
実施例ＸＶＩＩ
本実施例は、触媒が前駆体とビチューメン残油供給原料のアスファルテン留分との選択的化合の効果について示す。
【０１７４】
表１７は、１つは触媒を用い、１つは触媒を用いない２つのテストのデータを示す。これらのテストは、特に、アスファルテン転化率及びコークス収率の相違を実証した。２つの実験についてのピッチ転化率は類似していたが、アスファルテン転化率は約２倍異なり、触媒はアスファルテンを選択的に転化した。
【０１７５】
【表１７】

選択的アスファルテン転化率とコークス抑制に対する触媒前駆体の効果の追加の証拠は、表１８に示され、２つの＋５２５℃ハイドロクラッキング残油（ピッチ）組成を比較した。
【０１７６】
【表１８】

ピッチＩは、モリブデンアフタネート触媒前駆体を含むテストから得られた。ピッチＩＩは、モリブデンアフタネート触媒前駆体を含まないテストから得られた。
【０１７７】
図３８は、アスファルテン転化率は、４２〜９９％の広範囲のピッチ転化率について触媒の存在によって有利になったことを示す。触媒の存在下ではプロセスユニットは、清潔かつコークスが無い状態に保たれた。触媒の不存在下では、プロセスユニットは、コークスによって汚れた。
【０１７８】
【表１９】

実施例ＸＩＸ
本実施例は、触媒前駆体、モリブデンナフタネートがビチューメン残油の不存在又は存在下約３００℃以上の温度で分解することを示す。
【０１７９】
図３７のａ及びｂは、２５０℃以下の温度で安定であることを示す。図３７のｃは、触媒前駆体は、３００℃の温度で徐々に分解とポリマー化が始まることを示す。
【０１８０】
図３７のｄ及びｅは、ビチューメン残油に溶解した触媒前駆体は、２５０℃以下の温度で安定であることを示す。図３７のｆは、ビチューメンに溶解した触媒前駆体は、３００℃の温度で徐々に分解を始めたことを示す。
【０１８１】
触媒前駆体を３５０℃でビチューメン残油に注入することにより、モリブデン含有コークスを生じた。
【０１８２】
実施例ＸＸ
本発明の好ましい態様に従って（反応器生成物を処理する）、ホットセパレーターを離れた重質蒸留物とピッチの混合物を蒸留して、ピッチを生成した。このピッチの一部を反応器に循環した。
【０１８３】
このようにして以下のことを遂行した。
【０１８４】
（１）軽質分のストリッピングの速度は、水素フラックスの増加なしに増大し、循環流から軽質分は徐去された。これにより、コークス生成と触媒消費が減
少する。
【０１８５】
（２）循環流中のコロイド状の活性触媒は、反応器中に蓄積し、循環しない場合に比べて、より高い定常状態濃度が得られる。これにより循環しない場合に比べて触媒の消費は典型的には５０％減少する。
【０１８６】
（３）ピッチの滞留時間は選択的に増加して、それにより全液体収率は増加し、操作の安定性も向上する。
【０１８７】
さらに、少量の新しい原料をこの循環流に加えると、それにより、添加剤混合供給原料と混合する前にこの流れの混合と冷却が加速される。
【０１８８】
本実施例はこれらの特徴の実施の利点を示す。
【０１８９】
特に、図３９〜４１は、以下に説明する３段階テスト実験（Ｒ２−１）に用いた循環系と条件を示す。この実験は全部で４９０時間行った。
【０１９０】
実験Ｒ２−１の一般条件は以下のとおりである。
【０１９１】
原料：２００〜３６０℃軽油中に分散した１５０ｐｐｍのモリブデンエチ
ルヘキサノエートを含有するコールド・レーク真空残油
混合：窒素雰囲気下１０５℃で少なくとも２５時間の循環と混合を、原料
を工程へ送る前に行った。
【０１９２】
ハイドロクラッキング条件：
圧力 １３．６Ｍｐａ
温度 約４５０℃
Ｈ_２ 流 約１５，０００ｓｃｆ／バレル
蒸留：ＡＳＴＭ Ｐ−１１６０蒸留に従って行った。
【０１９３】
第一の段階（９６時間の操作）の間は、図３９に示すように、「１回通し」ベース、即ちピッチ循環なしにテストを行った。第２の段階では、原料の１５重量％の非転化のピッチを反応器に循環した。この第２の段階の工程は、図４０に示され、３９０時間続けた。非転化ピッチの循環は新しい原料ピッチの転化率を９０％（第１の段階）を９８％（第２の段階）に向上させた。
【０１９４】
実験Ｂ３−１（実施例ＩＸ）と比較して、実験Ｒ２−１では、顕著な閉塞や圧力振動は見られなかった。
【０１９５】
このことは、図４２及び４３の圧力記録に示されている。
【０１９６】
しかるに、循環用非転化ピッチの回収のためのホットセパレーターの生成の蒸留の間に、蒸留ポット中で（凝集物に似た）ピッチの塊りが生じた。これらの塊りは、除去が困難であり、蒸留容器中に強固に付着した。
【０１９７】
この塊りは、添加剤により形成したモリブデンスルフィドと非転化アスファルテンを含むことが分かった。１５０時間続けた実験であるこのテストの第３の段階では、新しい原料の一部を、蒸留容器に導入する前にホットセパレーターの生成物に添加した。この装置は図４１に示す。さらに、この第３の段階では、モリブデンへキサノエート濃度は１５０ｐｐｍ（金属）であった。
【０１９８】
第２の段階では、３１６４ｇのホットセパレーター生成物が８９．４ｇの塊状固体と２８．７ｇの蒸留ポットに強固に付着した残渣を生成したことが分かった。これは注入量の４．１％に相当した。
【０１９９】
第３の段階では、３２００．１ｇのホットセパレーター生成物と６０１．５ｇの新しいコールド・レーク真空残油とが塊りは生じず、かつ蒸留ポットに付着した、たった６．３ｇの残渣を生成した。これはホットセパレーター生成物の０．２％に相当した。
【０２００】
結論としてこのテストにより以下のことが得られた。
【０２０１】
○ この方法の条件により、閉塞及び汚れ無しに４９０時間操作することができた。
【０２０２】
○ 非転化ピッチの循環によりピッチ転化率が著しく増加した。
【０２０３】
○ ピッチ分離用の蒸留装置に新しい原料の一部を添加すると、蒸留工程におけるアスファルテンが減少した。換言すると、ホット循環ピッチへの新しい
原料の添加は、反応器への原料流への分散を加速した。
【０２０４】
本テストの終わりに、反応器とホットセパレーターは開放し、全てのユニットの表面が清潔かつ汚れが無いことが観察された。反応器から捕集された液体はろ過された。得られた固体は顕微鏡サイズの凝集物からなる細かい粉末であった。この得られた固体は、図４４に示す。
【０２０５】
【図面の簡単な説明】
【図１】等方性球体（ｓ）及び基本等方性粒子（ｂ）の特徴（粒子構造）を示す図面に代わる写真（倍率１６５０×）。
【図２】異方性球体（ｓ）及び基本異方性粒子（ｂ）の特徴（粒子構造）を示す図面に代わる写真（倍率１６５０×）。
【図３】異方性固体（ａ）と鉄スルフィド粒子（ｓ）を伴った等方性凝集物（ｇ）の特徴（粒子構造）を示す図面に代わる写真（倍率１６５０×）。
ここで鉄スルフィド粒子は原料から生成した。顕微鏡で検討されたコークス試料は鉄添加剤を用いない熱試験により生成した（図１７参照）。
【図４】異方性凝集物（ａ）、異方性微細モザイク（ｆ）と異方性粗モザイク（ｃ）の特徴（粒子構造）を示す図面に代わる写真（倍率１６５０×）。
【図５】より小さい異方性球体（ｃ）の合体により成長した異方性コークス粒子（粒子構造）を示す図面に代わる写真（倍率１６５０×）。
【図６】より小さい等方性球体（ｓ）の合体により成長した等方性コークス粒子（粒子構造）を示す図面に代わる写真（倍率１６５０×）。
【図７】実施例Ｉ（希釈剤Ｂ）に記載した実験ＣＦ−３０の後の反応器のバッフル板及びコークス析出物の図面に代わる写真（表２）。
【図８】実施例Ｉ（希釈剤Ａ）に記載した実験ＣＦ−９の後の反応器のバッフル板及びコークス析出物の図面に代わる写真（表２）。
【図９】実施例Ｉ（希釈剤Ｃ）に記載した実験ＣＦ−３１の後の反応器のバッフル板及びコークス析出物の図面に代わる写真（表２）。
【図１０】実験ＣＦ−９、ＣＦ−３１及びＣＦ−３０のコークス組成を示す棒グラフ。
【図１１】実施例ＩＩに記載した実験ＣＦ−Ａ３の後の反応器のバッフル板及びコークス析出物の図面に代わる写真（表３）。
【図１２】実施例ＩＩＩに記載した実験ＣＦ−Ａ３とＦＥ−１のコークス組成を示す棒グラフ。
【図１３】実験ＦＥ−１の後の反応器のバッフル板の図面に代わる写真。
【図１４】鉄スルフィドと化合した最も等方性の凝集物（Ａ）である実験ＦＥ−１からのコークス粒子（粒子構造）の図面に代わる写真。等方性球体（ｓ）は凝集物から採集した。
【図１５】鉄誘導体によって基本等方性粒子への成長が効果的に防止された等方性粒子（ｓ）を示す、実験ＦＥ−１からのコークス粒子（粒子構造）の図面に代わる写真。
【図１６】実施例ＩＶで記載した実験ＣＦ−３８の後の反応器バッフル板の図面に代わる写真。
【図１７】実施例Ｖでの窒素流速に対するコークス生成をプロットした図。
【図１８】実施例Ｖの相図である。
【図１９】実施例ＶＩＩＩで記載した異なる添加剤に関する実験の圧力変化をプロットした図。
【図２０】実施例ＶＩＩＩで記載した種々の実験についての消費水素を示す棒グラフ。
【図２１】実施例ＶＩＩＩで記載した番号の実験についてのコークス生成を示す棒グラフ。
【図２２】基本等方性粒子（Ｂ）の最も連続するシートを示す実験ＣＦ−４０からのコークス（粒子構造）の図面に代わる写真（倍率１６５０×、実施例ＶＩＩＩ参照）。
【図２３】実験ＣＦ−４０の後の反応器バッフル板及びコークス析出物の図面に代わる写真（Ａ）、及び実験ＣＦ−４１の後の反応器バッフル板及びコークス析出物の図面に代わる写真（Ｂ）。
【図２４】本発明に従って生成した触媒のモスバウアー顕微鏡分析により得られたプロットを示す図（実施例ＩＩＩ参照（表４））。
【図２５】実施例ＩＸで記載した実験の実施に用いたパイロットプラントの模式図（条件：原料と触媒前駆体（モリブデンエチルヘキサノエート溶液）をテストのスタート前２４時間以上１３５〜１５０℃の温度で混合及び循環させた）。
【図２６】実施例ＩＸの実験ＴＲＵ１０１の間に反応器とセパレーターの間のＰＴ４５５で記録された圧力変化を示す図。
【図２７】実施例ＩＸの実験ＴＲＵ１０１の間の反応器を横断するＤＰ４５０での差圧変化を示す図。
【図２８】実施例ＩＸの実験ＴＲＵ１０１の間に反応器入口のＰＴ４００において記録された圧力変化を示す図。
【図２９】実施例ＩＸの実験Ｂ３−１の間の反応器を横断するＤＰ４５０での差圧変化を示す図。
【図３０】実施例ＩＸの実験Ｂ３−１の間に、循環系に沿った異なるポイント（ＰＴ３４０、ＰＴ４００、ＰＴ４５５、ＰＴ５１０）における圧力変化を示す図。
【図３１】実施例Ｘで述べた実験の実施に用いたパイロットプラントの一部の模式図（記載された条件は、ビチューメン中でＦｅ（Ｃｏ）_５を分解させることにより、ビチューメンの鉄濃縮物を調製するために用いたもの）。
【図３２】実施例Ｘで述べた実験の実施に用いたパイロットプラントの一部の模式図（記載された条件は、Ｆｅ（ＣＯ）_５濃縮物の効果のテストに用いたもの）。
【図３３】実施例ＸＩで実施した実験の実施に用いたパイロットプラントの模式図。
【図３４】実施例ＸＩで実験についての圧力記録を示す図。
【図３５】実施例ＸＩＩで述べた実験の実施に用いたパイロットプラントの模式図（記載された条件で行った）。
【図３６】実施例ＸＩＩについて用いたプラントの反応器を横断する差圧、ヒーター中の圧力及び消化器温度の変化を示す図。
【図３７】実施例ＸＩＸにおける混合工程での温度の変化の効果を示す一連の（（ａ）〜（ｆ））のＩＲスペクトル。
【図３８】実施例ＸＶＩＩにおける４２と９９％の間のピッチ転化率を与える実験についてのアスファルテン転化率とピッチ転化率との関係を示す図。
【図３９】実施例ＸＸの実験Ｒ２−１の第１段階において用いた１回通しパイロットプラントの模式図（条件：原料と触媒前駆体（モリブデンエチルヘキサノエート溶液）をテストのスタート前２４時間以上、１１０℃未満の温度で混合及び循環させた）。
【図４０】実験Ｒ２−１の第２の段階で実施したピッチの循環を示す、図３９パイロットプラントを変形したものの模式図（条件：原料と触媒前駆体（モリブデンエチルヘキサノエート溶液）をテストのスタート前２４時間以上、１１０℃未満の温度で混合及び循環させた）。
【図４１】実験Ｒ２−１の第３の段階で実施したピッチの循環と原料の添加を示す、図４０のパイロットプラントをさらに変形したものの模式図（条件：原料と触媒前駆体（モリブデンエチルヘキサノエート溶液）をテストのスタート前２４時間以上、１１０℃未満の温度で混合及び循環させた）。
【図４２】実験Ｒ２−１の間に反応器を横断する差圧変化を示す図。
【図４３】実験Ｒ２−１の間にパイロットプラントに沿った異なるポイント（ＰＴ４００、ＰＴ４５５、ＰＴ５１０）における圧力変化を示す図。
【図４４】中央部に多数の粒子を取り込んだ外側の成分の融合又は合体の状態において実験Ｒ２−１から得た粒子（粒子構造）を示す図面に代わる写真（共焦顕微鏡写真）。高反射率のサブミクロンサイズの無機成分が、粒子の多数の領域で明らかに判別できる。（反射モード、６４７ｎｍ、油浸漬、２５００×）。[0001]
[Industrial applications]
The present invention is an improved method of reducing coke formation in hydrocracking of heavy oils, comprising the oil, a solvent for asphaltenes, and an oil-soluble metal compound, which interferes with coalescence of the coke precursor and provides an in-situ ( The mixture of (in situ) forming the catalyst particles) is heated and mixed at a mild temperature in the pretreatment, then introduced into the reactor and subjected to hydrocracking using a hydrogen-rich stream for mixing and efficient lightening. A method for ensuring minute stripping.
[0002]
BACKGROUND OF THE INVENTION
The present invention was originally developed for the hydrocracking of heavy hydrocarbon feedstocks having a high content of asphaltenes and sulfur. More specifically, the feedstock tested was vacuum tower resid (VTB) produced by the distillation of bitumen. The present invention is not limited to such a feedstock application, but will be described below with particular reference to highlighting the problems that need to be solved.
[0003]
Bitumen contains a relatively high proportion of asphaltenes. When bitumen or its vacuum tower resid is hydrocracked, asphaltenes form a coke precursor from which a sticky solid coke is formed. This coke deposits and adheres to the surfaces of the reactor and downstream equipment. In addition, the conversion of the feedstock to useful products is reduced as a portion of the feedstock is consumed in the production of coke.
[0004]
Applicant is Alberta Government Research Agency, which has been tasked with promoting improvements in the reforming of bitumen and other heavy oils.
[0005]
Applicants have recognized the limitations of conversion and have initiated a research project to address the problems posed by coke deposition and to investigate coke formation mechanisms and find improvements that could be economically applied. .
[0006]
The method was obtained as a result of this study. This work involved a refinement of the concept and experimental findings, which together provided a method characterized by reduced sticky coke deposition and reduced coke formation with high efficiency.
[0007]
Relevant prior art found in the search and procedure of the parent application of the present application is shown below.
[0008]
U.S. Pat. No. 4,294,686 (Fisher et al.) Discloses that when a liquid hydrogen donor oil is used with hydrogenation for the hydrocracking of bitumen vacuum tower resid, coke deposition is stated to be eliminated. I teach you that.
[0009]
Thus, Applicants and the Applicant have jointly conducted a large scale hydrocracking of bitumen resid using the liquid hydrogen donor method. This test faced a serious coke generation problem. According to it, a hydrocracked high asphaltene-containing feed such as bitumen resid requires more than the presence of a liquid hydrogen donor oil alone.
[0010]
U.S. Pat. No. 4,455,218 (Dimock et al.)₂(CO) as an in-situ generated catalyst source for hydrocracking of heavy oils in the presence of₅Teach the use of
[0011]
U.S. Pat. No. 4,485,004 (Fisher et al.) Teaches the hydrocracking of heavy oils in the presence of hydrogen, a hydrogen donor material and a catalyst comprising Ni or Co particles on alumina.
[0012]
U.S. Pat. No. 4,134,825 (Bielden et al.) Discloses an in situ solid non-colloidal catalyst in heavy oils using trace amounts of Fe added in the form of an oil-soluble compound such as iron carbonyl. Teach the formation. This metal compound is added to the oil and heated to 325-415 [deg.] C. while contacting with hydrogen to convert it to a solid, non-colloidal catalyst. This catalyst is then used in the hydrocracking of the oil, which states that coke formation is prevented.
[0013]
U.S. Pat. No. 4,592,827 (Gallerson et al.) Injects an oil-soluble catalyst precursor Mo compound and water into a stream of heavy oil traveling to a heater in which the mixture is heated from 230.degree. The Mo compound is heated to a temperature of ° C. to decompose the Mo compound. The heater product is then introduced into a hydrocracking reactor.
[0014]
[Means for Solving the Problems]
In one aspect of the work underlying the present invention, coke was prepared by hydrocracking a mixture of diluent and bitumen vacuum tower resid (VTB), and the coke composition was examined microscopically. As a result, it was found that different types of isotropic and anisotropic zabmicron and micron-sized spheroids were present in the process of converting the coke precursor to sticky solid coke. Several figures attached to this specification show these various spheroids and are labeled as follows.
[0015]
Isotropic sphere (Figures 1 and 6)
Basic isotropic particles (Fig. 1)
Isotropic aggregate (Fig. 3)
Anisotropic sphere (Figures 2 and 5)
Basic anisotropic particles (Fig. 2)
Anisotropic fine mosaic particles (Fig. 4)
Anisotropic coarse mosaic particles (Fig. 4) and
Anisotropic aggregate (Fig. 4)
Further, the following has been found by experiments.
[0016]
The conversion of coke precursor to coke involves the process of coalescing fine isotropic particles into larger particles (FIGS. 5 and 6) and
If the coalescence process is hampered by a major portion of the precursor remaining in the isotropic and anisotropic agglomeration state, the deposition of stickies and solid coke is significantly reduced and virtually eliminated.
[0017]
These observations indicate that the coalescence process is inhibited, and that if coke is present, it is desirable to reach an end goal that will predominantly exist in the form of aggregate species, preferably in an isotropic state. The search and identification of suitable additives to assist were made.
[0018]
A sufficiently dispersed and oil-soluble metal compound can react in situ with the sulfur content of the bitumen VTB to prevent the colloid particles from trapping the precursor spheroids on the surface and preventing the spheroids from coalescing. It was speculated that it could be used to produce colloidal catalyst particles with wax wetting properties. Further, it was speculated that a suitable diluent could be beneficially used to assist in dispersing this additive and solubilizing the precursor spheroids.
[0019]
Oil-soluble Mo, Fe, Ni, or Co compound additives such as iron pentacarbonyl or molybdenum 2-ethylhexanoate, which are degradable at the hydrocracking temperature and form particles that are hydrocracking catalysts in that case At a temperature of 50 to 300 ° C., preferably 80 to 190 ° C. and at a mild heating temperature below the decomposition temperature of the additive, resulting in a substantially uniform dispersion of the additive in the oil and Mixing for a time sufficient to ensure compounding with asphaltenes, and
It was experimentally found that if the resulting mixture was heated to the hydrocracking temperature and reacted in the reactor, the mechanism assumed above would occur.
[0020]
Otherwise, the incorporation of additives into the hydrocracked reaction mixture has the desired effect of reducing sticky solid coke deposition. However, the additives are sufficiently dispersed by the method described above. Testing of the cooled solid sample after hydrocracking indicated that the major part of the coke formed under these conditions was in the form of isotropic aggregates. It is believed that at the reaction temperature, this coke will take the form of fine spheroids of coke precursor. Chemical analysis of this sample coke indicated that a large amount of the added metal sulfide was combined with the coke and that most metal sulfides were colloidal, typically less than 0.1 nanometer in diameter. .
[0021]
In short, according to the present invention, the oil-soluble and decomposable metal compound as described above is first sufficiently mixed with heavy oil at a mild heating temperature, preferably using a diluent, to be combined with asphaltenes. It is believed that when the mixture is then brought to the hydrocracking temperature, colloidal metal sulfide particles are formed and accumulate on the surface of coke precursors or spheroids, inhibiting their coalescence. Upon completion of the hydrocracking, it is found that the coke precursor has largely changed to isotropic aggregates. In addition, it is also found that the deposition of sticky solid coke is significantly reduced.
[0022]
The experiments that follow show that:
[0023]
Additives are added to the oil at the reactor inlet or at a preheater immediately upstream of the reactor, and if prolonged mixing at a moderate temperature is not carried out, hydrocracking can be contaminated with coke. Be characterized.
[0024]
If mixing is performed for a long time, but is higher than the decomposition temperature of the additive, the resulting catalyst particles are relatively large (eg, 5 microns to 4 mm) and non-colloidal, in which case coke fouling To happen.
[0025]
If the oil used is bitumen, the bitumen usually contains sufficient solvent for asphaltenes and no addition of diluents or solvents is required.
[0026]
Preferred steps include the following steps.
[0027]
Mixing the oil, additives and preferably the asphaltenes solvent at a temperature in the range of 80-190C and below the decomposition temperature of the additives, for a time sufficient to uniformly disperse the dispersant;
Digesting at a heating temperature above the additive decomposition temperature and below the hydrocracking temperature while maintaining good dispersion while mixing the products; and
The mixture is heated to the hydrocracking temperature and it is introduced into the reactor.
[0028]
Testing whether the dispersion and digestion steps were performed properly for a sufficient amount of time and with sufficient agitation and at the appropriate temperature is confirmed by the conversion of the additive to colloidal sized catalytic metal sulfide particles. .
[0029]
The term "decomposition temperature" as used herein means the temperature at which less than about 10% by weight of an additive decomposes during the dispersion process.
[0030]
For the second method studied, it is well known that asphaltenes precipitate upon the addition of pentane. In view of this known fact, applicants considered emphasizing the removal of light during hydrocracking to determine the effect on coke formation. The experiment started by first determining the effect of stripping the light (boiling point (BP) <220 ° C) from the hydrocracking zone. Experiments have shown that coke formation was reduced when consistently removing light components during hydrocracking. In order to improve this point, it appeared desirable to mix the mixture during hydrocracking. Mixing also maintains the dispersion of the metal component of the additive.
[0031]
To further discuss the foregoing, it was considered that coke formation was associated with phase separation. It was speculated that the coke formation process proceeded quickly and quantitatively when the coke precursor was enriched in individual phases. In order to prevent this, it would be desirable to remove light components and reduce phase separation.
[0032]
Accordingly, a second preferred embodiment of the present invention uses a tubular reactor, preferably substantially free of packing, enriching the flow of hydrogen in the reactor, and occupying the entire length and width of the reaction zone. Adjusted to mix until. The abundant hydrogen stream serves to remove (strip) light from the region. Preferably, the mixing and removal is such that the flow of hydrogen is in the range of 8,000 to 20,000 SCF / BBL and is sufficient to achieve the following Pecklet Number (PN) in the reaction chamber: Done by
[0033]
liquid:
Axis P. N. = Less than 2.0, preferably less than 1.0, more preferably less than 0.01
gas:
Axis P. N. = Greater than 3.0, preferably greater than 5.0
As another method of reducing phase separation, a diluent to solubilize asphaltenes was added to the reaction mixture. The diluent (or solvent) has a B.I. of about 220-504 ° C, preferably 220-360 ° C. P. Was a hydrocarbon fraction having Solvents that have been successfully used are described by Jean Bichard, "Oil Sands Composition and Behaviour" (1987) pp. 2-30, Alberta Oil Sands. It had a high cot θ value as defined by the Alberta Oil Sands Technology and Research Authority (Edmont, Alberta, Canada).
[0034]
Preferred diluents included aromatic or cycloaliphatic but not aliphatic cyclic components. For example, n-hexane is not a good diluent, but cyclohexane, decalin and benzene are good diluents, the last being preferred. However, in the hydrocracker, less expensive than these diluents are the heavy aromatic fraction of hydrocracker gas oil at 220 ° C. to 360 ° C. or a similar fraction of unstabilized coke gas oil.
[0035]
The additive additionally serves usefully as a liquid hydrogen donor and, in combination with the formed colloidal metal sulfide (having catalytic properties) and abundant hydrogen, has a high boiling point (eg, 504 ° C.). It was desired to create conditions that favor high conversions of fractions and low coke precipitation. The experimental results show that the combination of diluent addition, addition of well-dispersed additives and removal of light components by hydrogen, when performed with respect to hydrocracking of heavy oils containing asphaltenes and sulfur, is substantially tacky. A particularly high conversion of high-boiling hydrocarbons was achieved without the precipitation of volatile coke. Experiments have shown significant coke deposition when the diluent is removed from the combination, or when the diluent is not a good solvent for asphaltenes, or when light components are not sufficiently removed. However, it should be understood that the addition of diluent is merely a preferred feature.
[0036]
In essence, the dispersion is, therefore, a process in which the mixture of heavy oil, additive and diluent is separated by continuous flow, means such as a stirred tank mixer, in a separate step prior to decomposition of the additive or heating to the hydrocracking temperature. Mixing (provided that the mixture is in the range of 50-300 ° C., preferably 80-190 ° C. and is kept at a temperature below the temperature at which the additives decompose significantly, and the residence time is such that the additives are substantially mixed in the mixture. Sufficient to ensure uniform distribution). For this mixing, the use of two or more continuous streams or continuous stirred tank reactors is also preferred.
[0037]
In a broad sense, one aspect of the present invention is a method for producing a heavy hydrocarbon feedstock for hydrocracking, comprising asphaltenes and sulfur, wherein the feedstock and the oil-soluble metal compound additive are treated at 50 ° C. To produce a product mixture by mixing at a temperature in the range of from about 300 ° C. and below the decomposition temperature of the additive, wherein the additive is selected from the group consisting of molybdenum, iron, nickel and cobalt compound additives. Wherein the additive decomposes when heated to a hydrocracking temperature, and reacts with sulfur in the feed to form metal sulfide particles that are a catalyst for hydrocracking; The metal sulfide particles formed by hydrocracking for a sufficient time to disperse the particles sufficiently to have a colloidal size. Including that.
[0038]
In another broad aspect, the invention is a method of hydrocracking a heavy hydrocarbon feedstock containing asphaltenes and sulfur, wherein the feedstock and the oil-soluble metal compound additive are treated at 50 ° C to 300 ° C. C. and mixed at a temperature lower than the decomposition temperature of the additive to prepare a product mixture, wherein the additive is selected from the group consisting of molybdenum, iron, nickel and cobalt compound additives. The additive decomposes when heated to a hydrocracking temperature, and reacts with sulfur in the feed to form metal sulfide particles that are a catalyst for hydrocracking; The metal sulfide particles formed by hydrocracking for a period of time sufficient to be dispersed into colloidal particles Then further heating the product mixture to the hydrocracking temperature, introducing the heated product mixture into the chamber of a hydrocracking reactor, temporarily holding the heated product mixture in the chamber, Continuously pass sufficient hydrogen to maintain mixing of chamber contents and stripping of light ends substantially across the width and length of the article, and unreacted hydrogen and Removing any remaining light from the chamber to produce a pitch-containing product comprising colloidal metal sulfide.
[0039]
In still another preferred embodiment of the present invention, the pitch is circulated from a downstream hot separator to the reactor to improve conversion. In a more preferred embodiment, the separator product comprising the heavy fraction and the pitch is distilled and the pitch is separately recovered, in which connection new feed is added to the separator stream entering the still, and the asphaltenes from the pitch are removed. Reduce separation. The addition of fresh oil is effective to reduce or prevent the formation of sticky asphaltenes that would otherwise appear in the still.
[0040]
In a preferred embodiment, the present invention involves the following units and conditions in a hydrocracking operation, see FIG.
[0041]
○ Thermal hydrocracker:
Operating temperature: 430-460 ° C, preferably 450-455 ° C;
Operating pressure: 1500-3000 psig, preferably about 2000 psig;
○ High pressure hot separator:
Operating temperature: about 350 ° C or higher;
Operating pressure: reactor pressure;
O Add 5-15% of new feedstock (heavy oil) to downstream from hot separator;
○ Low pressure hot separator:
Operating temperature: below the temperature of the hot separator;
Operating pressure: 100-500 psig;
○ Circulation of the 0-95% pitch from the low pressure hot separator to the reactor
[Description of preferred embodiments]
The feed to the process is a heavy oil. The term is meant to include derived oils from coal-petroleum co-processes, bitumen, and crude resids containing asphaltenes and sulfur. A typical feedstock may be derived vacuum tower resid from Athabasca bitumen.
[0042]
This feed is mixed with a catalyst precursor additive and preferably a hydrocarbon solvent for asphaltenes.
[0043]
This additive decomposes at the hydrocracking temperature and reacts with the sulfur in the oil to form in situ metal sulfide particles that are hydrocracking catalysts and interfere with coalescing of the coke precursor. It is an oil-soluble metal compound which has been improved. The metal can be selected from the group consisting of Fe, Ni, Co and Mo. Preferred compounds are iron pentacarbonyl and molybdenum 2-ethylhexanoate.
[0044]
The hydrocarbon solvent for asphaltenes preferably has a boiling point in the range of 220 ° C. to 504 ° C., preferably 220 ° C. to 360 ° C., and is described by Jean Bichard in “Oil Sands Composition and It is a circulating stream, preferably having a high value of the cot value θ, as defined in Oil Sands Composition and Behaviour.
[0045]
The amount of the additive ranges from 0.0001 to 5% by weight based on the weight of the raw material. Preferably we use about 0.002-0.5% by weight. The particular preferred compounds we use are typically:
[0046]
Molybdenum 2-ethylhexanoate 0.01% by weight
Molybdenum naphthalate 0.007% by weight
Iron pentacarbonyl 0.05% by weight
With respect to solvents for asphaltenes, some raw materials (eg crude atabasca bitumen) may already contain enough solvent so that no additional solvent is required. However, if solvent addition is required, the preferred weight ratio of solvent to raw material is in the range of 1:10 to 3: 1, preferably 1: 4 to 1: 1.
[0047]
Mixing can be performed in a continuous flow, heated, stirred tank mixer, or by transferring the mixture from a tank via a preheater and then returning to the tank. In any case, the mixing is performed according to the following conditions.
[0048]
Mixing temperature: a temperature within the range of 50-300 ° C., preferably 80-190 ° C., and at which less than about 10% by weight of the additives decompose during this mixing step;
Residence time: a time sufficient to ensure that the additive is substantially uniformly dispersed in the oil and substantially compounded with the asphaltenes at the molecular level.
[0049]
The method focuses on the use of iron pentacarbonyl and molybdenum 2-ethylhexanoate as preferred additives.
[0050]
In the case of iron pentacarbonyl, relatively large amounts need to be used to achieve satisfactory conversions. However, excessive use tends to form iron products which accumulate in the piping and cause blockage and pressure fluctuations. For proper use of iron pentacarbonyl, first disperse the additives in the oil at a mild temperature by mixing and then in the high-temperature digestion process under mixed conditions again to maintain the dispersion of the catalyst precursor It was found that it was desirable to do.
[0051]
Typically, iron pentacarbonyl as an additive and 504 ° C. as an oil⁺When bitumen vacuum tower bottoms are used, the following conditions are used.
[0052]
Additive amount: 250ppm (oil standard)
Solvent: 200-504 ° C bitumen fraction
Solvent / oil ratio: 1: 1.2
Dispersion time: 20 minutes
Dispersion temperature: 110 ° C
Dispersion container: 1 liter tank with impeller rotating at 800 rpm
Digestion time: 60 minutes
Digestion temperature: 250 ° C
Digestion container: 3.8 liter tank with impeller rotating at 1000 rpm
Typically, molybdenum 2-ethylhexanoate as an additive and 430 ° C. as an oil⁺The following conditions using bitumen vacuum tower bottoms are used.
[0053]
Additive amount: 150ppm
Solvent: 430-524 ° C distillate
Solvent / oil ratio: 1: 2
Dispersion time: 24 hours
Dispersion temperature: 100 ° C
Dispersion container: 75 liters
Digestion time: 60 seconds
Digestion: None
The mixture is then rapidly heated to about 450C to 455C and introduced into the hydrocracking reactor. In the reactor, the above-mentioned Peclet No. Hydrogen is supplied at a rate sufficient to satisfy the values and to ensure that mixing of the reactor charge occurs and that light or volatiles are removed from the charge.
[0054]
As an example, the following conditions were typically used for hydrocracking a mixture produced by a pilot plant using the mixing process described above.
[0055]
Reactor dimensions: Length 220.98 cm (87 inches) x diameter 4.50 cm (1.77 inches)
Reactor pressure: 1500 psig
Reactor temperature: 455 ° C
H₂Speed: 68 l / min
Mixing speed: 2405 g / hr
Distillate flow rate: 1082 g / hr
Pitch flow rate: 1322 g / hr
[The conversion was determined by the following formula.
[0056]
100% (inflow 524 ° C⁺Distillate outflow 524 ° C⁺Distillate) / (inflow 524 ° C⁺Fraction)
However, 524 ° C⁺The fraction does not contain inorganic substances but contains coke. ]
Fe (CO)₅In the case of experiments with additives, the pilot plant results under the above typical conditions show a typical 524 ° C.⁺The conversion of the fraction was 90%. The pitch was analyzed to contain colloidal iron sulfide. Coke production was about 1%.
[0057]
For experiments using molybdenum 2-ethylhexanoate, pilot plant results based on the above typical conditions show typical 524 ° C⁺The conversion of the fraction was 90%. The pitch contained colloidal iron sulfide. The coke production was about 0.3%.
[0058]
【Example】
Hereinafter, the present invention will be described based on examples and experimentally obtained data.
[0059]
Examples I to V
The following Examples IV are described to illustrate some of the features that were studied in the early stages of the method.
[0060]
All tests in Examples IV were performed in a 1 liter stirred autoclave with baffle plates. The packing is made up of Athabasca vacuum tower residue (504 ° C⁺), Solvents (or "diluents") and additives (if used) were introduced into the autoclave. The autoclave was sealed, evacuated and heated to 430 ° C. under pressure with nitrogen or hydrogen. The reactor was stirred at 800 rpm and reacted at a reaction temperature of 430 ° C. for 105 minutes.
[0061]
The properties of Athabasca vacuum tower residue (VTB) are as follows.
[0062]

Table 1 below shows the composition (% by weight) of the diluent used during the experimental procedure.
[0063]
It is noted that according to the relative contents of the fused dicycloparaffins and the benzenecycloparaffins, diluent B has the highest hydrogen donating capacity and diluent C has the lowest capacity.
[0064]
[Table 1]

Example I
This example describes the effect of different diluents. The autoclave contains 109 g of bitumen and 220 g of diluent A, B or C. A nitrogen overpressure of 0.55 MPa was applied and the contents were thermally cracked at 430 ° C. for 105 minutes.
[0065]
The test results are shown in Table 2. The reactor was opened and the coke deposited on the baffle plates of experiments CF-30, CF-9 and CF-31 are shown in FIGS. 7, 8 and 9, respectively.
[0066]
It is noted that although experiment CF-31 produced more coke than experiment CF-9, this coke was most easily removed from the baffle plate and reactor surface. In addition, experiment CF-31 produced about twice as much coke as CF-30, but this coke was most easily removed. The surfaces of the reactor and baffle plate of Experiment CF-31 were the least soiled.
[0067]
Coke from the three experiments was examined under a microscope and the results are shown in FIG. If the agglomerate concentration (which was anisotropic) was relatively high (Experiment CF-31), the coke deposition and sticking was the weakest, despite the fact that diluent C had the lowest hydrogen donating capacity. there were.
[0068]
[Table 2]

Example II
In this embodiment, the effect of the excess hydrogen pressure will be described.
[0069]
Table 3 shows the experimental conditions and results. Experiment CF-A3 is compared with experiment CF-9.
[0070]
FIG. 11 shows the coke deposited on the baffle plate of experiment CF-A3. The coke yield and precipitation of experiment CF-A3 were lower than in experiment CF-9 (FIG. 8).
[0071]
FIG. 12 shows the results of microscopic examination of coke obtained from experiment CF-A3. This is a comparison with the result shown in FIG. 10 of the experiment CF-9, and the result is the same.
[0072]
In both experiments, more than 80% of the coke component was of the anisotropic type. The experimental CF-A3 aggregation concentration was not significantly greater than that of experimental CF-9.
[0073]
This example teaches that the enrichment of hydrogen alone cannot neutralize the cohesiveness of the coke precursor or selectively modify the coke composition.
[0074]
[Table 3]

Example III
This example shows that coke containing many agglomerates is not sticky.
[0075]
Table 4 shows the results and conditions of Experiment CF-A3 and Experiment FE-1.
[0076]
FIG. 13 shows that no coke was deposited on the baffle plate of experiment FE-1. Compared with Experiment CF-A3 (FIG. 11), Experiment FE-1 has lower coke yield and precipitation.
[0077]
The coke from experiment FE-1 was observed to be fine particles that settled loosely at the bottom of the reactor.
[0078]
[Table 4]

FIG. 12 shows the results of microscopic examination of coke obtained from Experiment CF-A3 and Experiment FE-1. These results are very different. Over 80% of the coke from experiment FE-1 is isotropic aggregates.
[0079]
Figures 14 and 15 of Experiment FE-1 showed that the solid particles were all weakly combined with each other. Coke composition indicated that over 97% of the components were anisotropic. (See FIG. 12). Isotropic aggregates were 80% of the coke composition. .
This data for experiment FE-1 indicated that the coke precursor tack was efficiently neutralized by the highly dispersed iron compound. When the isotropic spheres were concentrated (see FIG. 15), the isotropic aggregates effectively prevented the spheres from coalescing into the basic isotropic particles.
[0080]
It is also noted that the additives present as iron sulfides account for about one third of the coke weight but are not very apparent.
[0081]
Example IV
This example further illustrates that the choice of diluent is desirable.
[0082]
Experiment CF-38 was performed according to the teachings of U.S. Patent No. 4,455,218 (Dimock et al.). The experimental conditions are the same as those shown in Table 4 for experiment FE-1. All Athabasca bitumen was used in place of Athabasca VTB and no diluent was added. All bitumens contained about 60% by weight of hydrocarbons boiling above 504 ° C. 504 ° C in bitumen⁺0.5% (metal) of iron pentacarbonyl was added on an equivalent basis of the content.
[0083]
The coke yield is 7.9% (504 ° C.⁺This coke adhered very strongly to the surface of the reactor and the baffle plate. FIG. 16 shows the coke deposited on the baffle plate.
[0084]
Example V
This example illustrates the effect of the rate of continuous removal of highly volatile components from the reaction fluid.
[0085]
Put 1 N autoclave in reactor₂Or H₂And a cold trap cooler for removing volatile products from the gas stream before the gas was collected in a sample bag for analysis. The experiments were carried out in the reactor at 430 ° C. for 105 minutes, at a pressure of 550 kPa, without gas flow and with a continuous gas flow inside and outside the reactor. In each experiment, 110 g of atabasca 504 ° C⁺Vacuum tower resid (VTB) and 220 g of diluent were used. Table 5 below shows the reaction conditions and experimental results.
[0086]
[Table 5]

[Table 6]

FIG. 17 shows coke production as a function of nitrogen flow rate. As shown for diluents A and B, coke production decreased with increasing nitrogen flow rate. At high nitrogen flow rates, the amount of coke produced in the experiment with diluent B (the best hydrogen donor solvent) was very different from that in the experiment with diluent B (the worst hydrogen donor solvent). There was no.
[0087]
In Table 5, it is noted that, for the conditions that give low coke production, the amount of condensate recovered from the exhaust gas was the highest. This is true for both diluents A and B.
[0088]
Table 6 shows the results of the simulated distillation of the condensate from Run 5. About 90% of this condensate boils at temperatures below 220 ° C.
[0089]
This example shows that coke production decreases as low boiling products are continuously removed (stripped) from the reaction fluid. In addition, coke production is shown to decrease as low boiling products are removed from the diluent.
[0090]
These observations are consistent with a model that has asphaltenes separation as a separate liquid phase from the reaction fluid. Similar to the general experiment of adding pentane to bitumen to obtain solid asphaltenes at room temperature, experiments performed at such high temperatures are expected to yield asphaltenes as a separate liquid phase. Further, it is expected that this separated liquid phase will be rich in asphaltenes that thermally decompose to form coke.
[0091]
This phase separation is schematically shown in FIG. The three components in this figure are labeled asphaltene aromatic, aliphatic and cycloaliphatic at 504 ° C.⁺, 220 to 504 ° C and 220 ° C, respectively. Arrows indicate the occurrence of total bitumen composition that would have occurred in Example IV.
[0092]
Example VI
This example demonstrates the effect of using hydrogen to continuously remove highly volatile components from the reaction fluid.
[0093]
A continuous flow system consisting of a preheater, a 2 liter stirred reactor and a product collection system was used. The baffle plate and stirrer are similar to those of the previous example. A mixture of Athabasca VTB, diluent A and preheated hydrogen was pumped through the preheater to the bottom of the stirred reactor. The product was removed via a dip tube whose inlet was set at 60% of the height of the reactor.
[0094]
The experimental conditions and results are shown in Table 7 for Experiments 7, 8 and 9. In each experiment, the hydrogen flow rate was 12 slpm. In Experiment 7, the liquid hourly space velocity is twice that of Experiments 8 and 9. The temperature of the reaction fluid is 20 ° C. higher than that of Experiment 8.
[0095]
It should be noted that although the severity of hydrocracking increased from Experiments 7 to 8, and even 9, the amount of coke produced in Experiment 8 was less than in Experiment 7 and almost no coke was produced in Experiment 9. It was not.
[0096]
Such results would be expected if one considers that the highly volatile fraction of the reaction fluid is removed with increased efficiency when the conditions are changed from experiments 7 to 8, and even to 9. In experiment 9, the pipe connecting the reactor to the product collector was clogged at the end of the experiment.
[0097]
In experiment 10, two 1 liter reactors were placed side by side, with dip tube inlets at 50% and 70% of the reactor height. Table 7 shows the conditions and results.
[0098]
[Table 7]

The conversion was similar to Experiment 8. This is expected to give different liquid hourly space velocities and different numbers of reactors. However, despite the high hydrogen flow rate in Experiment 10, the amount of coke produced in Experiment 10 was greater than the amount produced in Experiment 8.
[0099]
This example teaches that the hydrogen stream and reaction temperature could be successfully used to remove (strip) low boiling products from the reaction fluid and reduce the amount of coke produced. Further, for a series of one or more hydrocracking reactors, one reactor teaches that the arrangement produces only small amounts of coke. In addition, it teaches that arranging multiple hydrocracking reactors side by side will reduce coke production as volatile hydrocarbons are removed from the fluid as one moves from one reactor to the next.
[0100]
Example VII
This example demonstrates that high conversion of VTB to distillation products due to reactor geometry, reaction severity, stripping of volatiles and the successful use of additives results in acceptable coke formation and minimal reactor , Indicating that it can be obtained.
[0101]
The continuous flow system of Experiments 7, 8 and 9 of Example VI was used. The additive was iron pentacarbonyl. Table 8 shows the conditions and results of Experiments 11 and 12.
[0102]
The conditions of Experiment 12 were much more severe than those of Experiment 11. Nevertheless, all surfaces of the reactor, pipes and collection vessel were clean of coke and the resulting coke was a fine, friable product that settled in the product collection vessel.
[0103]
Table 9 shows the microscopic test results of the coke produced in Experiment 12. 74% of the coke was in the form of agglomerates. Although 23% of the coke was in the form of isotropic spheres, these spheres were sequestered and trapped in an aggregate matrix.
[0104]
This example teaches that if the majority of the coke formed is agglomerates, high conversions will be obtained with minimal reactor fouling.
[0105]
[Table 8]

In experiment 12, H₂It should be noted that if the stream did not increase, a 14% increase in conversion would have been expected with a coke yield significantly higher than the amount recorded.
[0106]
[Table 9]

Example VIII
In this example, various additives and various metal compounds were compared.
[0107]
In a series of tests using the following additives, a comparison of their considerable efficiency in preventing coke formation and precipitation was made.
[0108]
○ Fine Alberta (Charcoal)
○ Oil-soluble nickel naphthalate
○ oil-soluble cobalt naphthalate, and
○ Oil-soluble molybdenum naphthalate
Iron pentacarbonyl was used as a reference for comparison.
[0109]
All tests were performed under the following general reaction conditions.
[0110]
0.5% by weight (metal, based on vacuum tower bottoms) additive, Athabasca vacuum tower bottoms (33.3%), diluent (66.7%), 6.8 Mpa initial hydrogen pressure, 800 rpm stirring speed, 430 ° C and a reaction time of 105 minutes. In the case of Alberta charcoal, the amount added was an amount corresponding to 4% of the vacuum tower bottoms.
[0111]
The pressure curve in FIG. 19 and the hydrogen consumption result in FIG. 20 show the following observation order for hydrogen consumption.
[0112]
Molybdenum additive (CF-40) 68%
Nickel additive (CF-41) 39%
Cobalt additive (CF-41) 27%
Iron additive (FE-1) 26%
And charcoal (CF-43) 21%
The product dispersions in Table 10 showed the following additive order.
[0113]
○ Vacuum tower residue conversion
Molybdenum> Iron> Charcoal> Nickel> Cobalt
○ C₅-504 ° C selectivity
Nickel> Iron> Cobalt> Molybdenum> Charcoal
○ Coke generation
Nickel <Cobalt <Charcoal <Iron <Molybdenum
FIG. 21 shows the effectiveness of various additives in converting coke precursors to form non-precipitating isotropic aggregate coke particles. Experiments with the molybdenum-containing additive consumed the largest amount of hydrogen, but over 90% of the coke was elementally isotropic particles. In FIG. 22, the coke from experiment CF-40 appeared as a continuous sheet of basic isotropic particles. Coke from experiment CF-40 was clearly more densely packed than coke from experiment FE-1 with the iron additive (FIGS. 14-15).
[0114]
As indicated above, the additives must selectively convert the coke precursor spheres into isotropic aggregates to prevent coke deposition on the reactor walls. The absence of isotropic aggregates in the coke from experiment CF-40 suggests an explanation for the deposition of sticky coke on the reactor baffle plate (FIG. 23). On the other hand, there was no sticky coke in the reactor baffle plate (FIG. 13) in the experiment using iron pentacarbonyl.
[0115]
This example teaches that by appropriate choice of additives, coke formation can be prevented and, with the use of a suitable diluent, sticky coke will be prevented from depositing. Such additives minimize the coke fraction in the form of isotropic agglomerates. Oil-soluble additives comprising iron or cobalt or nickel or combinations thereof are preferred.
[0116]
[Table 10]

Examples IX to XII
These examples generally support the following assertions.
[0117]
1. Dispersion of the additive must be performed at a temperature lower than the decomposition temperature, and long-time mixing at a mild heating temperature is required to uniformly disperse the additive in the asphaltenes.
[0118]
2. Digestion, which causes degradation of additives, must be performed under mixed conditions. further,
3. The combination of said additive selection, preferred use of solvent, dispersing and digesting steps, and stripping and mixing during hydrocracking, together make the high 525 ° C. with little sticky coke formation⁺Produces colloidal catalyst particles that allow for conversion.
[0119]
In other words, if the additives are not well dispersed on a molecular scale before significant decomposition occurs, it is likely that relatively large, non-colloidal, submicron sized catalyst particles will form and sticky There will be formation of coke and conversion will be low. Similarly, if the decomposition of the additive occurs without mixing to maintain dispersion, a non-colloidal catalyst will be formed, resulting in coke and a lower conversion.
[0120]
Example IX
This example (for experiments TRU101 and B3-1) shows that it is desirable to properly disperse the additives by mixing them for an extended period of time at a heating temperature that is well below the decomposition temperature of the additives. Otherwise, if the mixture is then rapidly heated to the hydrocracking temperature, severe fouling may occur in the heater or at the reactor inlet, causing blockage, which is characterized by fluctuations in pressure in the circulation. Attached.
[0121]
FIG. 25 shows the system used for these tests. FIGS. 26-28 show the pressure records obtained during experiment TRU 101 at the points indicated on FIG.
[0122]
Pumps and return pipes were provided in the mixing and dispersing vessels ("mixers") to allow the raw materials to circulate and mix. Hydrogen from the source was added to a tube that removed the product from the mixer. The mixture was heated through a heater to raise the temperature to the hydrocracking temperature. The heater product was then introduced into a hydrocracking reactor. The reactor product produced pitch through a hot separator.
[0123]
The conditions for the first experiment (TRU101) are shown below.
[0124]

The mixer was initially operated at 135 ° C. for 17.1 hours from start. The mixer temperature was then raised to 150 ° C. (below the additive decomposition temperature). 25.9 hours after start, the first pressure oscillation was observed at PT455, suggesting that a weak blockage occurred downstream of the inlet to the hot separator. At 85.3 hours after the start, pressure oscillation to 16.3 Mpa was observed at PT320, suggesting that a slight occlusion occurred between PT320 and PT340. Upon opening the obstruction, pressure oscillations were observed at DP450, indicating that the obstruction was extruded through the reactor and downstream to the hot separator. 99 hours after the start, the pressure at PT400 oscillated to 15.2 Mpa, indicating that a blockage had formed at the entrance to the reactor. After 108.9 hours from start, PT400 and upstream pressure jumped to 21.6 Mpa due to the formation of a strong blockage at the reactor inlet.
[0125]
These results give the following observations:
[0126]
The occlusion was not a problem when the dispersion was performed at 135 ° C, but became a problem at 150 ° C. further
Decomposition of the additives occurred in or around the heater under non-mixing conditions. This causes the formation of large iron particles that plug the pipe.
[0127]
The same system was used for experiment B3-1. The conditions for this experiment are as follows.
[0128]

Experiment B3-1 lasted 225 hours. There were the following differences as compared to the experimental TRU101.
[0129]
○ The dispersion temperature was low.
[0130]
○ The additive concentration decreased to a certain extent.
[0131]
○ The reactor temperature was slightly low.
[0132]
The pressure recording of experiment B3-1 is shown in FIGS.
[0133]
Smooth, unobstructed operation was observed during virtually all tests. After about 160 hours, the pressure upstream of the separator oscillated slightly to about 19.0 Mpa due to blockage and rupture. The blockage and fouling of the unit was significantly less in Experiment B3-1 than in Experiment TRU101.
[0134]
This experiment shows that it is desirable to disperse at a much lower temperature due to the decomposition temperature and to rapidly heat to the hydrocracking temperature.
[0135]
Example X
This example shows that good results are not obtained when additives are added at high concentrations in the oil and when the dispersion is carried out at a high temperature above the decomposition temperature.
[0136]
In this test, the dispersion and decomposition took place in one paragraph at the first site, and the mixed product was transferred to another site for hydrocracking. A concentration (4 wt% Fe) was formed at the first site to facilitate transfer. The two circulatory systems used are shown in FIGS.
[0137]
Experimental conditions are shown with the drawings.
[0138]
Some experimental results in this system are as follows.
[0139]
[Table 11]

According to electron microscopic analysis of the solid from the formed pitch, the FeSx particles typically had a diameter of 5 μm.
[0140]
Pitch conversion (57-68%) was relatively poor and coke was formed in the reactor circulation.
[0141]
Example XI
This example is an addition to Example X, and when bitumen and the additive are digested only at the decomposition temperature without being preliminarily mixed at a low temperature, good results can be obtained by digestion while mixing. Indicates that it cannot be performed.
[0142]
FIG. 33 shows a pilot circulation system, and several conditions were used in this experiment. FIG. 34 shows a pressure record for this experiment.
[0143]
The conditions in this test are as follows.
[0144]
○ Supply: Athabasca bitumen, composition: 45% 220-524 ° C, 55% 525 ° C⁺
○ Feeding speed: 2.815 kg / hr
○ Additive: 33% by weight iron pentacarbonyl in light oil
○ Addition rate: 32.9 ml / hr
○ Additive concentration: 525 ° C⁺5000 ppm based on the fraction
○ Hydrogen: 34 standard liters / minute (4000 SCF / BBL)
○ Digestion temperature: 250 ℃
○ Reactor conditions: 450 ° C, 10.2 Mpa
The pressure drop across the reactor increased gradually during the experiment and increased sharply after 33 hours. The circulatory system became inoperable 36 hours after the recording pressure at PT23A increased.
[0145]
Testing of the material filtered from the formed pitch indicated that the iron sulfide particle size was 1-2 μm.
[0146]
Example XII
This example demonstrates good conversion and coke reduction when the proper dispersion is performed at a mild or mild temperature, well below the additive decomposition temperature, and when the decomposition is performed with mixing. Indicates that a reduction result is obtained.
[0147]
FIG. 35 shows the circulation system and conditions used in this experiment. FIG. 36 shows various records from the experiment.
[0148]
In this test, bitumen and iron pentacarbonyl were mixed in a first vessel with an impeller at a temperature of about 100 ° C. for about 30 minutes to disperse the additives and then in a second vessel with an impeller for about 250 minutes. The mixture was mixed at a temperature of about 1 hour for about 1 hour and decomposed while dispersing.
[0149]
Table 12 below shows other conditions and experimental results.
[0150]
[Table 12]

The first 100 hours of operation was smooth and no obstruction was seen. At that point the pump failed. After the repair, a slight perturbation was recorded in the pressure drop across the reactor, but the operation of the circulation was quite successful. The pitch conversion gradually increased from 84% to 92% during about 300 hours of the experiment.
[0151]
Tests have shown the additive iron to be present in the pitch in the form of colloidal iron sulfide particles.
[0152]
Example XIII
This example provides data showing the extent of decomposition of molybdenum naphthalate ("Mo-naph") and molybdenum ethyl hexanoate ("Mo-HEX") at different temperatures.
[0153]
Specifically, infrared spectra of bitumen samples containing either Mo-naph or Mo-HEX were measured at 130 ° C, 200 ° C, and 300 ° C for a certain period of time. The following table shows the percent decomposition of each of these catalyst precursors as a function (%) of the respective spectral component that disappeared at a given time.
[0154]
[Table 13]

Example XIV
This example shows that the catalyst particles produced by the method of the present invention are colloidal in size.
[0155]
Samples of the pitch generated in experiment CFE-1 were examined by X-ray diffraction and a Mossbauer spectrometer.
[0156]
FeS by X-ray diffraction test₂The existence of was revealed.
[0157]
FIG. 24 shows the spectrum of Mossbauer analysis. Confirmation data is provided in Table 14 below. The width of each peak in the spectrum is important. Such widths indicate very fine colloidal particles, typically less than 10 nanometers in diameter.
[0158]
Prior to this test, chemical analysis showed more than 20% by weight of iron sulfide in the pitch, but microscopic examination of a sample of pitch obtained from experiments performed in accordance with the present invention showed no evidence for iron sulfide particles. Did not. This evidence indicates that the catalyst particles are submicroscopic in size.
[0159]
[Table 14]

Examples XV to XIX
These examples are based on experiments using molybdenum naphthalate as an additive or catalyst precursor.
[0160]
In the experiment, vacuum tower resid from bitumen was used as a raw material. The properties and composition of the raw materials are as follows.
[0161]
[Table 15]

The circulatory system used in the reported experiment is that of FIG. Molybdenum naphthalate was added to the raw material to give 300 ppm molybdenum. The feed was agitated and pumped through a loop tube at 200 ° C. for 3 hours before the experiment. The test was performed for 12 to 15 hours.
[0162]
Example XV
This example shows that high asphaltene conversion with minimal formation of solid coke is obtained when the present invention is practiced using molybdenum naphthalate as an additive.
[0163]
Cold Lake Vacuum resid asphaltene-rich feedstock (IBP above 430 ° C) 0.01 m³Into a surging tank.
[0164]
Molybdenum naphthalate was added to the above tank equipped with a stirrer and a circulation pump so that the molybdenum content became 300 ppm, and mixed at 200 ° C. under a nitrogen atmosphere to form a uniform mixture. This mixture was pumped into the reactor via a process heater. The temperature was raised to 455 ° C. in the process heater. Hydrogen was added to the mixture at the inlet of the process heater. Hydrogen was supplied at a rate of 10,000 to 12,000 SCF / BBL and a pressure of 2000 psig. The process heater had an inner diameter (ID) of 2.9 mm and a length of 6100 mm immersed in tin at a hydrocracking temperature.
[0165]
The capacity of the hydrocracking reactor is 669cm³Met. It was a stainless steel cylinder with an inner diameter (ID) of 25 mm and a height of 1370 mm.
[0166]
The conditions for the operation of the reactor are as follows.
[0167]
H₂/ Volume flow of liquid = 10,000 SCF / BBL
Liquid pecullet no. = About 0.25
Gas speclet No. = About 6
(These pellet numbers are Xe¹³³And I¹³¹Determined from a tracer test using )
LHSV is 0.4-1.0h^-1Met. It usually took 10-12 hours for the reactor to reach steady state operating conditions. Hydrocracking was performed at a temperature of 455 ° C. and a pressure of 2000 psig. The reactor effluent containing the gas and liquid mixture was sent to a hot separator that separated the gas and liquid.
[0168]
Table 16 shows typical results of the method.
[0169]
[Table 16]

The hydrocracking test was performed on the cold lake vacuum resid listed in Table 15 and the precursor concentration was 300 ppm Mo based on the raw material. After each test, all units in the experimental system were opened and inspected to ensure that they were free of coke and other soil.
[0170]
It should be noted that the experiments using Mo performed well without solvent, despite using VTB as the raw material.
[0171]
Example XVI
This example shows that the catalyst of Example XV was colloidal.
[0172]
The hydrocracking resid was dispersed in methylene chloride and the mixture was injected on a gel permeation column. The molybdenum-containing component was found to have a distinct molecular weight range of 400 to 3000 for this gel permeation column calibrated with polystyrene. This range corresponds to colloidal particles having a diameter greater than or equal to 0.002 microns and less than or equal to 0.01 microns.
[0173]
Example XVII
This example shows the effect of the selective combination of the catalyst with the asphaltene fraction of the bitumen resid feedstock.
[0174]
Table 17 shows data from two tests, one with and one without catalyst. These tests demonstrated, inter alia, differences in asphaltene conversion and coke yield. Although the pitch conversions for the two experiments were similar, the asphaltenes conversions differed about two-fold, and the catalyst selectively converted asphaltenes.
[0175]
[Table 17]

Additional evidence of the effect of the catalyst precursor on selective asphaltene conversion and coke control is shown in Table 18 and compared the two + 525 ° C. hydrocracking resid (pitch) compositions.
[0176]
[Table 18]

Pitch I was obtained from a test involving a molybdenum aphthanate catalyst precursor. Pitch II was obtained from a test that did not include the molybdenum aphthanate catalyst precursor.
[0177]
FIG. 38 shows that asphaltene conversion was favored by the presence of the catalyst for a wide range of pitch conversions from 42-99%. In the presence of the catalyst, the process unit was kept clean and free of coke. In the absence of a catalyst, the process unit was fouled by coke.
[0178]
[Table 19]

Example XIX
This example shows that the catalyst precursor, molybdenum naphthalate, decomposes at temperatures above about 300 ° C. in the absence or presence of bitumen resid.
[0179]
FIGS. 37 a and b show that they are stable at a temperature of 250 ° C. or less. FIG. 37c shows that the catalyst precursor begins to decompose and polymerize gradually at a temperature of 300 ° C.
[0180]
FIGS. 37 d and e show that the catalyst precursor dissolved in the bitumen resid is stable at temperatures below 250 ° C. FIG. 37f shows that the catalyst precursor dissolved in bitumen began to decompose gradually at a temperature of 300 ° C.
[0181]
Molybdenum-containing coke was produced by injecting the catalyst precursor at 350 ° C. into the bituminous resid.
[0182]
Example XX
In accordance with a preferred embodiment of the present invention (treating the reactor product), the mixture of heavy distillate and pitch leaving the hot separator was distilled to produce pitch. Part of this pitch was circulated to the reactor.
[0183]
Thus, the following was accomplished.
[0184]
(1) The stripping rate of the light increased without increasing the hydrogen flux, and the light was gradually removed from the circulation. This reduces coke generation and catalyst consumption.
Less.
[0185]
(2) The colloidal active catalyst in the circulating stream accumulates in the reactor, and a higher steady-state concentration is obtained as compared to the case without circulation. This typically reduces the catalyst consumption by 50% compared to the case without circulation.
[0186]
(3) Pitch residence time is selectively increased, thereby increasing overall liquid yield and operating stability.
[0187]
In addition, the addition of a small amount of fresh feed to the recycle stream accelerates the mixing and cooling of this stream prior to mixing with the additive blend feed.
[0188]
This embodiment illustrates the advantages of implementing these features.
[0189]
In particular, FIGS. 39 to 41 show the circulation system and conditions used in the three-stage test experiment (R2-1) described below. This experiment was performed for a total of 490 hours.
[0190]
The general conditions of the experiment R2-1 are as follows.
[0191]
Raw material: 200 to 360 ° C 150 ppm molybdenum ethylene dispersed in light oil
Cold Lake Vacuum Residue Containing Luhexanoate
Mixing: circulation and mixing at 105 ° C. for at least 25 hours under a nitrogen atmosphere
Was carried out before sending to the process.
[0192]
Hydrocracking conditions:
Pressure 13.6Mpa
Temperature approx. 450 ° C
H₂Flow about 15,000 scf / barrel
Distillation: performed according to ASTM P-1160 distillation.
[0193]
During the first phase (96 hours of operation), the test was performed on a "single pass" basis, i.e., without pitch circulation, as shown in FIG. In the second stage, 15% by weight of the feed, unconverted pitch was circulated to the reactor. This second stage process is shown in FIG. 40 and lasted 390 hours. Circulation of the unconverted pitch increased the conversion of the new feed pitch from 90% (first stage) to 98% (second stage).
[0194]
Compared with Experiment B3-1 (Example IX), in Experiment R2-1, remarkable blockage and pressure oscillation were not observed.
[0195]
This is shown in the pressure records of FIGS. 42 and 43.
[0196]
However, during the distillation of the formation of the hot separator for recovery of the unconverted pitch for circulation, agglomeration of the pitch (similar to agglomerates) occurred in the distillation pot. These lumps were difficult to remove and adhered strongly in the distillation vessel.
[0197]
This mass was found to contain molybdenum sulfide and unconverted asphaltenes formed by the additive. In the third stage of this test, an experiment lasting 150 hours, a portion of the new feed was added to the hot separator product before being introduced into the distillation vessel. This device is shown in FIG. Further, in this third stage, the molybdenum hexanoate concentration was 150 ppm (metal).
[0198]
In the second stage, it was found that 3164 g of the hot separator product produced 89.4 g of a bulk solid and a residue that adhered strongly to a 28.7 g distillation pot. This corresponded to 4.1% of the injection volume.
[0199]
In the third stage, 3200.1 g of hot separator product and 601.5 g of fresh cold lake vacuum resid produced no lumps and only 6.3 g of residue adhered to the distillation pot. . This represented 0.2% of the hot separator product.
[0200]
In conclusion, this test yielded the following:
[0201]
○ The conditions of this method allowed operation for 490 hours without blockage and contamination.
[0202]
○ Pitch conversion increased significantly due to circulation of non-converted pitch.
[0203]
○ Asphaltene in the distillation process was reduced by adding some of the new raw materials to the distillation apparatus for pitch separation. In other words, a new hot circulating pitch
Feed addition accelerated dispersion into the feed stream to the reactor.
[0204]
At the end of the test, the reactor and hot separator were opened and it was observed that the surfaces of all units were clean and free of dirt. The liquid collected from the reactor was filtered. The resulting solid was a fine powder consisting of microscopic aggregates. The resulting solid is shown in FIG.
[0205]
[Brief description of the drawings]
FIG. 1. Characteristics of isotropic sphere (s) and basic isotropic particles (b)(Particle structure)ShowSubstitute drawingPhotograph (magnification 1650x).
FIG. 2 Characteristics of anisotropic spheres (s) and basic anisotropic particles (b)(Particle structure)ShowSubstitute drawingPhotograph (magnification 1650x).
FIG. 3. Characteristics of an isotropic aggregate (g) with anisotropic solid (a) and iron sulfide particles (s)(Particle structure)ShowSubstitute drawingPhotograph (magnification 1650x).
Here, iron sulfide particles were produced from the raw material. Coke samples examined under a microscope were generated by a thermal test without iron additives (see FIG. 17).
[FIG. 4] Features of anisotropic aggregates (a), anisotropic fine mosaics (f) and anisotropic coarse mosaics (c)(Particle structure)ShowSubstitute drawingPhotograph (magnification 1650x).
FIG. 5 shows anisotropic coke particles grown by coalescence of smaller anisotropic spheres (c).(Particle structure)ShowSubstitute drawingPhotograph (magnification 1650x).
FIG. 6 isotropic coke particles grown by coalescence of smaller isotropic spheres (s)(Particle structure)ShowSubstitute drawingPhotograph (magnification 1650x).
FIG. 7: Baffle plate and coke deposits of the reactor after experiment CF-30 as described in Example I (Diluent B)Substitute drawingPhoto (Table 2).
FIG. 8: Baffle plate and coke deposits of the reactor after experiment CF-9 described in Example I (Diluent A)Substitute drawingPhoto (Table 2).
FIG. 9: Baffle plate and coke deposits of the reactor after experiment CF-31 as described in Example I (diluent C)Substitute drawingPhoto (Table 2).
FIG. 10 is a bar graph showing the coke composition of experiments CF-9, CF-31 and CF-30.
FIG. 11 shows the reactor baffle plate and coke deposits after experiment CF-A3 described in Example II.Substitute drawingPhoto (Table 3).
FIG. 12 is a bar graph showing the coke composition of experiments CF-A3 and FE-1 described in Example III.
FIG. 13 shows the reactor baffle plate after experiment FE-1.Substitute drawingPhoto.
FIG. 14: Coke particles from experiment FE-1, the most isotropic aggregate (A) combined with iron sulfide(Particle structure)ofSubstitute drawingPhoto. Isotropic spheres (s) were collected from the aggregates.
FIG. 15: Coke particles from experiment FE-1 showing isotropic particles (s) whose growth into basic isotropic particles was effectively prevented by the iron derivative(Particle structure)ofSubstitute drawingPhoto.
FIG. 16 shows a reactor baffle plate after experiment CF-38 described in Example IV.Substitute drawingPhoto.
FIG. 17 is a diagram plotting coke generation with respect to a nitrogen flow rate in Example V.
FIG. 18 is a phase diagram of Example V.
FIG. 19 is a plot of the pressure change of the experiment for the different additives described in Example VIII.
FIG. 20 is a bar graph showing hydrogen consumption for the various experiments described in Example VIII.
FIG. 21 is a bar graph showing coke generation for the numbered experiments described in Example VIII.
FIG. 22: Coke from experiment CF-40 showing the most continuous sheet of basic isotropic particles (B)(Particle structure)ofSubstitute drawingPhotograph (magnification 1650x, see Example VIII).
FIG. 23 shows reactor baffle plates and coke deposits after experiment CF-40.Substitute drawingPhoto(A), And of reactor baffle plate and coke deposits after experiment CF-41Substitute drawingPhoto(B).
FIG. 24 shows a plot obtained by Mossbauer microscopic analysis of the catalyst produced according to the invention (see Example III (Table 4)).
FIG. 25 is a schematic view of a pilot plant used for carrying out the experiment described in Example IX (conditions: raw material and catalyst precursor (molybdenum ethyl hexanoate solution) were heated at 135 to 150 ° C. for at least 24 hours before the start of the test. Mixed and circulated at temperature).
FIG. 26 shows the pressure change recorded at PT 455 between the reactor and the separator during the experimental TRU 101 of Example IX.
FIG. 27 shows the change in differential pressure at DP450 across the reactor during experiment TRU101 of Example IX.
FIG. 28 shows the pressure change recorded at PT400 at the reactor inlet during experiment TRU101 of Example IX.
FIG. 29 shows the change in differential pressure at DP450 across the reactor during experiment B3-1 of Example IX.
FIG. 30 is a diagram showing pressure changes at different points (PT340, PT400, PT455, PT510) along the circulatory system during experiment B3-1 in Example IX.
FIG. 31 is a schematic view of a part of a pilot plant used for performing the experiment described in Example X (the conditions described are Fe (Co) in bitumen;₅Used to prepare a bitumen iron concentrate by dissolving
FIG. 32 is a schematic diagram of a part of a pilot plant used for performing the experiment described in Example X (the conditions described are Fe (CO)₅Used to test the effect of the concentrate).
FIG. 33 is a schematic view of a pilot plant used for performing the experiment performed in Example XI.
FIG. 34 shows pressure recordings for an experiment in Example XI.
FIG. 35 is a schematic diagram of a pilot plant used for performing the experiment described in Example XII (under the conditions described).
FIG. 36 shows changes in differential pressure across the reactor of the plant, pressure in the heater and digester temperature used for Example XII.
FIG. 37 is a series of ((a) to (f)) IR spectra showing the effect of temperature change in the mixing step in Example XIX.
FIG. 38 is a diagram showing the relationship between asphaltene conversion and pitch conversion for an experiment giving a pitch conversion between 42 and 99% in Example XVII.
FIG. 39 is a schematic diagram of a once-through pilot plant used in the first stage of experiment R2-1 in Example XX (conditions: starting material and catalyst precursor (molybdenum ethyl hexanoate solution) 24 hours before start of test) As mentioned above, it was mixed and circulated at a temperature of less than 110 ° C.)
FIG. 40 is a schematic diagram of a modified version of the pilot plant of FIG. 39 showing the pitch circulation performed in the second stage of experiment R2-1 (conditions: raw material and catalyst precursor (molybdenum ethyl hexanoate solution) were tested) For at least 24 hours before the start of the process at a temperature of less than 110 ° C.).
FIG. 41 is a schematic view of a further modification of the pilot plant of FIG. 40 showing the pitch circulation and the addition of the raw material performed in the third stage of experiment R2-1 (conditions: raw material and catalyst precursor (molybdenum ethyl hexa Noate solution) was mixed and circulated at a temperature below 110 ° C. for at least 24 hours before the start of the test).
FIG. 42 shows the change in differential pressure across the reactor during experiment R2-1.
FIG. 43 shows pressure changes at different points (PT400, PT455, PT510) along the pilot plant during experiment R2-1.
FIG. 44. Particles obtained from experiment R2-1 in the state of fusion or merging of outer components incorporating a large number of particles in the center.(Particle structure)ShowPictures that replace drawings (Confocal micrograph). Sub-micron sized inorganic components with high reflectivity are clearly discernable in many areas of the particle. (Reflection mode, 647 nm, oil immersion, 2500 ×).

Claims (12)

A method for producing a heavy hydrocarbon oil feedstock for hydrocracking, comprising asphaltenes and sulfur,
(A) the oil feedstock and the oil-soluble metal compound additive decomposable at an elevated temperature at a concentration of less than 0.5% by weight of the oil feedstock in a range of 50 ° C to 300 ° C; Mixing at a temperature below the decomposition temperature of the additive to prepare a product mixture;
[However, the additive is a molybdenum compound, decomposes by heating, and when heated to a hydrocracking temperature, reacts with sulfur in the oil feedstock to form molybdenum sulfide particles that are a hydrocracking catalyst. To do
The mixing comprises (i) binding the oil-soluble additive to the asphaltenes, and (ii) the colloidal size of the molybdenum sulfide particles in the oil feedstock, resulting in (iii) During hydrocracking of the feedstock, a period of time sufficient to prevent coke formation is provided. ]
(B) heating the product mixture to a height not temperature than the decomposition temperature of the oil-soluble additive, said additive to decompose while it is combined with the asphaltenes, it is reacted with a sulfur content of the oil feedstock Forming colloidal sized molybdenum sulfide particles . The method of claim 1 wherein the product mixture is heated to a hydrocracking temperature in step (b) to form the colloidal sized molybdenum sulfide particles. Introducing the product mixture into a chamber of a hydrocracking reactor; and
The product mixture is temporarily held in the chamber and is sufficient to maintain mixing and stripping of the light contents substantially across the width and length of the chamber contents. 3. The method of claim 2, comprising continuously passing hydrogen to remove unreacted hydrogen and residual light from the chamber to produce a pitch-containing product comprising colloidal metal sulfide. 4. The method of claim 3, comprising adding a hydrocarbon solvent for asphaltenes to the oil feed and additives during initial mixing. The method according to any one of claims 1 to 4, wherein the mixing in step (a) is performed at a temperature ranging from 80C to 190C. The method according to any one of claims 1 to 5, wherein the oil-soluble metal compound additive comprises molybdenum 2-ethylhexanoate or molybdenum naphthalate. The method according to any one of claims 1 to 6, wherein the molybdenum sulfide particles have a size of less than 0.1 nm. The process according to any one of the preceding claims, wherein a circulating stream having a boiling point in the range of 220C to 504C is added to the oil feed as a hydrocarbon solvent for the asphaltenes. 9. The method of claim 8, wherein the circulating stream has a boiling point in the range of 220C to 360C. The process according to claim 8 or 9, wherein the ratio of hydrocarbon solvent to oil feed is in the range of 1:10 to 3: 1. The method according to claim 10, wherein the ratio of hydrocarbon solvent to oil feed is in the range of 1: 4 to 1: 1. 12. The method according to any of the preceding claims, wherein the oil-soluble metal compound additive is mixed with the oil feed at a concentration of less than 0.05% by weight of the oil feed. Method.

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