公开(公告)号：US4889699A

公开(公告)日：1989-12-26

申请号：US208933

申请日：1988-06-20

Applicant: Mitri S. Najjar ,  Michael W. Becker

Inventor： Mitri S. Najjar ,  Michael W. Becker

IPC: C01B3/38 ,  C10J3/46

CPC classification number: C10J3/463 ,  C01B3/386 ,  C10J3/466 ,  C01B2203/0255 ,  C01B2203/0415 ,  C01B2203/0465 ,  C01B2203/0485 ,  C01B2203/0877 ,  C01B2203/1247 ,  C01B2203/1258 ,  C01B2203/1276 ,  C01B2203/145 ,  C01B2203/148 ,  C10J2300/0983

Abstract: Synthesis gas is produced by the partial oxidation of a feedstock comprising sulfur and ash-containing heavy liquid hydrocarbonaceous fuels, solid carbonaceous fuels, or mixtures thereof. An iron-containing additive is introduced into the reaction zone along with the feed to produce first and second liquid phase washing agents that collect and transport the vanadium-containing oxide laths and spinels and other ash components out of the reaction zone. A gaseous slag fludizing agent is also introduced into the top of the reaction zone so tha the gasifier is operated at a uniform temperature throughout under conditions that maximize the fluidity of the molten slag over the full opereating temperature range in the gasifier. Equilibrium oxygen and sulfur concentrations are provided in the gas phase in the reaction zone which provide specific partial pressures. By this method substantially all of the molten slag having a reduced viscosity and containing the nickel and vanadium-containing impurities from the feedstock are readily removed from the walls of the gas generator at a lower temperature. Simultaneously, in-situ desulfurization of the feedstock takes place in the gasifier so that the raw effluent product gas may leave the gasifier containing less than about 1.00 mole % of H.sub. 2 S and COS. In one embodiment, an additional supplemental gas e.g. free-oxygen, H.sub.2 S, COS, SO.sub.2, and mixtures thereof may be introduced into the gasifier so as to increase the carbon conversion without increasing the temperature in the reaction zone; or to prevent the formation of free-iron.

Abstract translation: 通过包含硫和含灰分的重液体含烃燃料，固体碳质燃料或其混合物的原料的部分氧化来生产合成气。 将含铁添加剂与进料一起引入反应区，以产生第一和第二液相洗涤剂，其将含钒氧化物板条和尖晶石和其它灰分组分收集并输送出反应区。 气态渣渣剂也被引入反应区的顶部，因此气化器在气化器中在整个运行温度范围内最大限度地提高熔渣流动性的条件下，在均匀的温度下运行。 在提供特定分压的反应区中的气相中提供平衡的氧和硫浓度。 通过这种方法，在较低温度下，基本上所有具有降低粘度并且含有来自原料的含有镍和钒的杂质的熔渣容易从气体发生器的壁中除去。 同时，在气化器中进行原料的原位脱硫，使得原始流出物产物气体可能离开含有小于约1.00摩尔％的H 2 S和COS的气化器。 可以将游离氧，H 2 S，COS，SO 2及其混合物引入气化器中，以增加碳转化率而不增加反应区中的温度; 或防止形成游离铁。

公开(公告)号：US4889658A

公开(公告)日：1989-12-26

申请号：US208929

申请日：1988-06-20

Applicant: Mitri S. Najjar

Inventor： Mitri S. Najjar

IPC: B01J23/755 ,  C01B3/36 ,  C01B3/38 ,  C01B32/40 ,  C10J3/46

CPC classification number: C01B3/386 ,  B01J23/755 ,  C01B3/363 ,  C10J3/466 ,  C01B2203/0255 ,  C01B2203/0415 ,  C01B2203/0465 ,  C01B2203/0485 ,  C01B2203/0877 ,  C01B2203/1247 ,  C01B2203/1258 ,  C01B2203/1276 ,  C01B2203/145 ,  C01B2203/148 ,  C10J2300/0983 ,  Y02P20/52

Abstract: Synthesis gas is produced by the partial oxidation of a feedstock comprising a high silicon and sulfur-containing heavy liquid hydrocarbonaceous fuel and/or petroleum coke or tar sands having nickel and vanadium-containing ashes in admixture with a silicon and manganese-containing ash fusion temperature modifying agent in a vertical free-flow unobstructed reaction zone lined with a refractory which comprises in wt. %: silicon-containing material about 95 to 99.8, iron oxide about 0.1 to 1.0, Al.sub.2 O.sub.3 about 0.1 to 1.0, CaO about 0 to 0.4, and others about 0 to 1.2. In the reaction zone separate portions of said silicon and manganese-containing additive (i) combine with a portion of said Fe, Ni, and S to generate a first liquid phase washing agent which washes a portion of the high melting vanadium and oxide phases from the reaction zone, (ii) combine with a portion of said Ni, Ca, Si, Al, Mg and Na and/or K to generate a liquid oxide-silicate phase that fluxes and washes substantially all of the remaining vanadium and other ash components, and (iii) combine with a portion of the molten ash from the fuel and a minor portion of the refractory lining said reaction zone to increase the amount of said liquid oxide silicate phase and thereby enhance the removal of the vanadium from said reaction zone. By this method molten slag having a reduced viscosity and containing the nickel and vanadium-containing impurities from the feedstock and refractory components are readily removed from the gas generator.

Abstract translation: 合成气通过含有高含硅和含硫的重质液体烃类燃料和/或具有含镍和含钒灰分的石油焦或焦油砂的原料的部分氧化产生，其中含有含硅和含锰灰分熔融温度 在耐火材料内衬的垂直自由流动无障碍反应区中的改性剂，其含量以重量计。 ％：含硅材料约95〜99.8，氧化铁约0.1〜1.0，Al2O3约0.1〜1.0，CaO约0〜0.4，其他约0〜1.2。 在反应区中，所述含硅和含锰添加剂的分离部分（i）与所述Fe，Ni和S的一部分组合以产生第一液相洗涤剂，其将一部分高熔点钒和氧化物相从 反应区，（ii）与所述Ni，Ca，Si，Al，Mg和Na和/或K的一部分组合以产生液体氧化物 - 硅酸盐相，其基本上全部剩余的钒和其它灰分组分 ，和（iii）与来自燃料的熔融灰分的一部分和所述反应区的耐火衬里的一小部分结合，以增加所述液体氧化硅酸盐相的量，从而增强从所述反应区除去钒。 通过这种方法，具有降低的粘度并且含有来自原料和难熔组分的含镍和钒的杂质的熔渣容易从气体发生器中除去。

公开(公告)号：US4851152A

公开(公告)日：1989-07-25

申请号：US242588

申请日：1988-09-12

Applicant: Mitri S. Najjar

Inventor： Mitri S. Najjar

IPC: C01B17/06 ,  C10J3/46

CPC classification number: C01B17/06 ,  C10J3/466 ,  C10K1/16 ,  C01B2203/0255 ,  C01B2203/0415 ,  C01B2203/045 ,  C01B2203/0485 ,  C01B2203/0877 ,  C01B2203/0883 ,  C01B2203/0894 ,  C01B2203/127 ,  C01B2203/148 ,  C10J2300/0959 ,  C10J2300/0983 ,  C10J2300/1223 ,  C10J2300/1846

Abstract: A sulfur-containing heavy liquid hydrocarbonaceous fuel and/or solid carbonaceous fuel with nickel, vanadium, and silicon containing ashes is mixed with a copper and/or cobalt-containing material to provide a weight ratio of copper and/or cobalt to nickel in the range of about 0.2 to 10; and the weight ratio of copper and/or cobalt to silicon in said mixture is in the range of about 0.0001 to 0.04. The mixture is reacted by partial oxidation in a down-flowing free-flow unobstructed vertical reaction zone with refractory lined walls at a temperature in the range of about 1800.degree. F. to 2900.degree. F., an equilibrium oxygen concentration in the gas phase in the reaction zone with a partial pressure in the range of about 1.7.times.10.sup.-15 to 2.3.times.10.sup.-8 atmospheres; and an equilibrium sulfur concentration in the gas phase in the reaction zone with a partial pressure in the range of about 2.53.times.10.sup.-7 to 8.1.times.10.sup.-2 atmospheres. A raw effluent gas stream is produced comprising H.sub.2 +CO and containing entrained slag comprising the following phases: (i) Cu-Ni or Co-Ni alloy, (ii) copper silicate and/or cobalt silicate, (iii) a spinel phase, and (iv) about 0 to 5 wt. % of a fluid oxysulfide phase. Substantially no toxic Ni.sub.3 S.sub.2 is produced in the slag.

Abstract translation: 含有镍，钒和含硅灰分的含硫重质液体含烃燃料和/或固体碳质燃料与铜和/或钴的材料混合，以提供铜和/或钴与镍的重量比 范围约0.2〜10; 所述混合物中铜和/或钴与硅的重量比在约0.0001至0.04的范围内。 在约1800°F至2900°F的温度范围内，在具有耐火内衬壁的下流自由流无障碍垂直反应区中，通过部分氧化使混合物反应，气相中的平衡氧浓度 反应区的分压在约1.7×10-15至2.3×10-8大气压的范围内; 和反应区气相中的平衡硫浓度，其分压在约2.53×10-7至8.1×10-2大气压的范围内。 生产包含H 2 + CO并含有夹带炉渣的原料流出物流，其包含以下相：（i）Cu-Ni或Co-Ni合金，（ii）硅酸铜和/或硅酸钴，（iii）尖晶石相， 和（iv）约0至5wt。 ％的流体硫氧化物相。 在渣中基本上没有产生有毒的Ni3S2。

公开(公告)号：US4681700A

公开(公告)日：1987-07-21

申请号：US727968

申请日：1985-04-26

Applicant: Stephen R. Vasconcellos ,  Mitri S. Najjar ,  Ralph Garcia

Inventor： Stephen R. Vasconcellos ,  Mitri S. Najjar ,  Ralph Garcia

IPC: C10J3/46

CPC classification number: C10J3/466 ,  C10J3/526 ,  C10J3/74 ,  C10J3/78 ,  C10J3/84 ,  C10J2300/0943 ,  C10J2300/0956 ,  C10J2300/0959 ,  C10J2300/1807 ,  C10J2300/1846

Abstract: An aqueous dispersion of unreacted particulate petroleum coke substantially comprising carbon and containing a small amount of ash substantially comprising vanadium constituents and other materials from a process for the partial oxidation of petroleum coke to produce synthesis gas is mixed with C.sub.4 to C.sub.8 acyclic and/or cyclic alkanols and a frothing agent. After pH adjustment, if necessary, the mixture is subjected to aeration with or without mechanical agitation in a froth flotation zone. About 60 to 95 wt. % of the unconverted particulate petroleum coke (basis carbon) particles float in the froth layer that is formed. The remainder of the unconverted petroleum coke comprising coarser particles is suspended in a bottom aqueous dispersion on which the froth layer floats. In addition, selective separation of the vanadium constituents in the unconverted petroleum coke ash takes place. The vanadium content of the ash in the floated portion of unconverted petroleum coke is unexpectedly decreased about 40 to 80 weight percent. Simultaneously, the vanadium content of the ash in the unconverted petroleum coke suspended in the bottom layer of aqueous dispersion is unexpectedly increased about 20 to 60 weight percent. Water may be recovered from this aqueous dispersion and recycled to the gas quench cooling and scrubbing zones. At least portions of the unconverted particulate petroleum coke from the foam layer and the bottom layer are recycled to the partial oxidation gas generator and to a vanadium recovery zone, respectively. By the subject process, the vanadium content in the recycle stream of unconverted petroleum coke to the gas generator is reduced. The life of the refractory lining of the gas generator is thereby extended.

Abstract translation: 将来自石油焦部分氧化生产合成气的方法中基本上含有碳并含有少量灰分的少量灰分的未反应颗粒状焦油的水分散体与C4至C8无环和/或环状 链烷醇和起泡剂。 pH调节后，如果需要，混合物在泡沫浮选区进行机械搅拌或无机械搅拌。 约60〜95重量％ 未转化的颗粒状石油焦炭（基础碳）颗粒的％漂浮在形成的泡沫层中。 将包含较粗颗粒的未转化的石油焦炭的其余部分悬浮在泡沫层浮起的底部水分散体中。 另外，在未转化的石油焦炭中进行钒成分的选择性分离。 未转化的石油焦的漂浮部分中的灰分的钒含量意外地下降了约40至80重量％。 同时，悬浮在水分散体底层的未转化的石油焦炭中的灰分的钒含量意外地增加约20至60重量％。 可以从该水分散体中回收水并再循环至气体骤冷冷却和洗涤区。 来自泡沫层和底层的未转化的颗粒状石油焦的至少一部分分别再循环到部分氧化气体发生器和钒回收区。 通过本发明方法，未转化的石油焦炭与气体发生器的再循环流中的钒含量降低。 从而延长了气体发生器耐火衬里的使用寿命。

公开(公告)号：US4671804A

公开(公告)日：1987-06-09

申请号：US803264

申请日：1985-11-29

Applicant: Mitri S. Najjar

Inventor： Mitri S. Najjar

IPC: C01B3/36 ,  C10J3/46

CPC classification number: C10J3/463 ,  C01B3/36 ,  C10J3/466 ,  C10J2300/0983 ,  Y10S48/07

Abstract: Synthesis gas is produced by the partial oxidation of a fuel feedstock comprising sulfur-containing petroleum coke and/or heavy liquid hydrocarbonaceous fuel and having a nickel and iron-containing ash in a free-flow refractory lined partial oxidation reaction zone. The production of toxic nickel subsulfide (Ni.sub.3 S.sub.2) in said slag is prevented, and there is a substantial reduction in the concentration of H.sub.2 S+COS in the raw product gas stream by introducing an iron-containing additive into the reaction zone along with the feed. The weight ratio of iron-containing additive to ash in the fuel feedstock is in the range of about 0.5 to 10.0. The weight ratio of iron to nickel in said mixture of iron-containing additive and fuel feedstock is greater than 0.33. The additive combines with at least a portion of the nickel and iron constituents and sulfur found in the feedstock to produce a very fluid sulfide phase of iron and nickel, and an Fe, Ni alloy phase. In another embodiment, a minor amount of a calcium compound is included with the iron-containing additive only at startup to reduce the softening temperature of the iron-containing addition agent. By this method, the molten slag produced is free from toxic Ni.sub.3 S.sub.2 and has a comparatively reduced viscosity. Further, the slag may be readily removed from the gas generator at a lower temperature and may be disposed of without contaminating the environment. Further, the life of the refractory lining is extended.

Abstract translation: 通过在自由流动耐火材料内衬的部分氧化反应区中含有含硫石油焦和/或重液态含烃燃料并具有含镍和铁的灰分的燃料原料的部分氧化产生合成气。 在所述炉渣中生产有毒的二硫化镍（Ni3S2），并且通过将含铁添加剂与进料一起引入反应区域，可以显着降低原料气流中的H 2 S + COS的浓度。 燃料原料中含铁添加剂与灰分的重量比在约0.5至10.0的范围内。 所述含铁添加剂和燃料原料混合物中铁与镍的重量比大于0.33。 添加剂与原料中发现的镍和铁成分和硫的至少一部分结合，以产生非常流动的铁和镍的硫化物相以及Fe，Ni合金相。 在另一个实施方案中，仅在启动时仅含铁添加剂含有少量钙化合物以降低含铁添加剂的软化温度。 通过该方法，所生成的熔渣不含有毒的Ni3S2，粘度相对降低。 此外，渣可以在较低温度下容易地从气体发生器中移出，并且可以在不污染环境的情况下进行处理。 此外，耐火衬里的寿命延长。

公开(公告)号：US4668429A

公开(公告)日：1987-05-26

申请号：US749376

申请日：1985-06-27

Applicant: Mitri S. Najjar

Inventor： Mitri S. Najjar

IPC: C01B3/38 ,  C10J3/46 ,  C07C3/36

CPC classification number: C01B3/386 ,  C10J3/463 ,  C10J3/466 ,  C10J2300/0983

Abstract: Synthesis gas is produced by the partial oxidation of a feedstock comprising petroleum coke and/or heavy liquid hydrocarbonaceous fuel containing sulfur and having an ash that contains nickel, vanadium and a comparatively high level of silicon. An iron and calcium-containing additive is introduced into the reaction zone along wth the feed. Separate portions of the additive (i) combine with a portion of the nickel, calcium and sulfur to generate a liquid phase washing agent that collects and transports out of the gas generator a portion of the vanadium-containing oxide laths and spinels and other ash components; and (ii) combine with a portion of the nickel, calcium and silicon to generate a liquid oxide-silicate phase that fluxes e.g. dissolves substantially all of the remaining portion of said vanadium-containing oxide laths and spinels and other ash components. In another embodiment, a minor amount of an additonal material selected from the group of elements consisting of magnesium, chromium, manganese, and mixtures thereof is included in the iron and calcium-containing additive. In still another embodiment, the iron and calcium-containing additive is uniformly dispersed in petroleum coke having a nickel and vanadium-containing ash. By this method two types of molten slag having reduced viscosities and containing the nickel and vanadium-containing impurities from the feedstock are readily removed from the gas generator at a lower temperature. Further, the life of the refractory lining is extended.

Abstract translation: 合成气体是通过包含石油焦和/或含有硫的重液态含烃燃料并含有含有镍，钒和较高含量硅的灰分的原料的部分氧化而产生的。 含铁和钙的添加剂沿着进料沿引入反应区。 添加剂的单独部分（i）与镍，钙和硫的一部分组合以产生液相洗涤剂，其从气体发生器收集和输出一部分含钒氧化物板条和尖晶石和其它灰分 ; 和（ii）与镍，钙和硅的一部分结合以产生液体氧化物 - 硅酸盐相， 基本上溶解所有含钒氧化物板条和尖晶石和其它灰分的剩余部分。 在另一个实施方案中，在含铁和钙的添加剂中包括少量选自镁，铬，锰及其混合物的元素组的添加材料。 在另一个实施方案中，含铁和钙的添加剂均匀分散在具有含镍和含钒灰分的石油焦炭中。 通过该方法，在较低温度下容易地从气体发生器中除去具有降低的粘度并且含有来自原料的含镍和钒的杂质的两种熔渣。 此外，耐火衬里的寿命延长。

公开(公告)号：US5358553A

公开(公告)日：1994-10-25

申请号：US726434

申请日：1991-07-05

Applicant: Mitri S. Najjar ,  Tansukhlal G. Dorawala ,  Uygur Koturk

Inventor： Mitri S. Najjar ,  Tansukhlal G. Dorawala ,  Uygur Koturk

IPC: B01D71/02 ,  C01B3/50 ,  B01D53/22 ,  B01D69/04 ,  C25D13/00

CPC classification number: B01D67/0069 ,  B01D71/022 ,  C01B3/505 ,  B01D2323/08 ,  C01B2203/0405 ,  C01B2203/048 ,  Y10S55/05

Abstract: Mixtures of hydrogen and hydrocarbons may be separated by a membrane formed of a thin dense layer of platinum or palladium on the inside of a porous graphite tube.

Abstract translation: 氢和烃的混合物可以通过在多孔石墨管的内部由铂或钯的薄致密层形成的膜分离。

公开(公告)号：US5318688A

公开(公告)日：1994-06-07

申请号：US28894

申请日：1993-03-05

Applicant: Mitri S. Najjar ,  Carl A. Hultman

Inventor： Mitri S. Najjar ,  Carl A. Hultman

IPC: B01D71/02 ,  C01B3/50 ,  C25D3/66 ,  B01D39/00 ,  B32B7/00 ,  C25D

CPC classification number: B01D67/0069 ,  B01D71/022 ,  C01B3/505 ,  C25D3/66 ,  B01D2325/023 ,  C01B2203/0405 ,  C01B2203/048

Abstract: Gases such as hydrogen/hydrocarbon may be separated by a separating membrane of a Group VIII noble metal on a deposit of non-noble Group VIII metal which is supported on a porous silver or a porous carbon body.

Abstract translation: 诸如氢/烃的气体可以通过负载在多孔银或多孔碳体上的非贵金属VIII族金属的沉积物上的VIII族贵金属的分离膜分离。

公开(公告)号：US5183482A

公开(公告)日：1993-02-02

申请号：US717790

申请日：1991-06-19

Applicant: Mitri S. Najjar ,  Martin D. Hilmar

Inventor： Mitri S. Najjar ,  Martin D. Hilmar

IPC: B01D53/22 ,  B01D71/02

CPC classification number: B01D67/0048 ,  B01D53/22 ,  B01D53/228 ,  B01D71/02 ,  B01D2325/02

Abstract: Mixture of gases such as hydrogen/carbon dioxide may be separated by use of membrane formed by reaction of an aluminum alkoxide with steam at high temperatures and pressures.

Abstract translation: 气体如氢气/二氧化碳的混合物可以通过使用由烷醇铝与蒸汽在高温和高压下反应而形成的膜来分离。

公开(公告)号：US5106811A

公开(公告)日：1992-04-21

申请号：US590745

申请日：1990-10-01

Applicant: Arnulf Muan ,  Mitri S. Najjar

Inventor： Arnulf Muan ,  Mitri S. Najjar

IPC: B01J23/847 ,  B01J37/08

CPC classification number: B01J23/8472 ,  B01J37/08 ,  Y10S502/524

Abstract: The present invention pertains to novel vanadium spinel materials and a method for their preparation. Each vanadium spinel material has a trivalent vanadium cation and is crystallized from a liquid having a composition that falls within a specific polygon shaped area in a ternary composition diagram of V.sub.2 O.sub.3 -FeO-SiO.sub.2 as shown in the drawing herein e.g., FIG. 1. The compositions may be used as a catalyst for oxidation reactions.

Abstract translation: 本发明涉及新型钒尖晶石材料及其制备方法。 每个钒尖晶石材料具有三价钒阳离子，并且在V 2 O 3 -FeO-SiO 2的三元组成图中从具有落入特定多边形区域内的组成的液体中结晶，如图所示。 该组合物可用作氧化反应的催化剂。