125 results about "Ultra-low-sulfur diesel" patented technology

An improved method for desulfurizing a fuel stream such as a diesel stream is disclosed which includes generation of a sulfone oil, the desulfurization of the sulfone oil and the recycling of the resulting biphenyl-rich stream and ultra-low sulfur diesel streams. The method includes combining a thiophene-rich diesel stream with an oxidant to oxidize the thiophenes to sulfones to provide a sulfone-rich diesel stream. Sulfone oil is extracted from the sulfone-rich diesel stream to provide sulfone oil and a first low-sulfur diesel stream The low-sulfur diesel stream is recycled. The sulfone-rich oil stream is combined with an aqueous oxidant-containing stream, such as caustic stream, which oxidizes the sulfones to biphenyls and forms sulfite to provide a second low-sulfur diesel stream

The invention relates to a preparation method of catalyst by ultralow-sulfur hydrofining. Al2O3-SiO2-ZrO2 tertiary compound oxide as a carrier, W-Mo-Ni-Co quaternary elements as active metal components and P as aid are used to prepare the catalyst which is butterfly-shaped. The preparation method is characterized by introducing SiO2 to Al2O3 to modulate surface acidity of the carrier and increasing specific surface area and pore volume of the carrier; introducing ZrO2 to increase low-temperature reactivity of the catalyst; preparing metallic co-impregnated solution by complexing process, and loading W-Mo-Ni-Co quaternary active metal components and the aid P by means of stepwise saturated impregnation to increase dispersity and utilization rate of active metals. The catalyst has the advantages of large specific surface, large pore volume, moderate surface acidity, high metal reduction activity and high low-temperature reactivity. Compared with like catalysts, the catalyst can be used to produce ultralow-sulfur diesel with lower than 10microgram / g sulfur content under low reaction severity.

The invention discloses a grading method of catalyst of deep hydrodesulfurization of diesel oil, comprising the following steps: base oil and hydrogen are mixed, then the mixture is led into a hydrogenation reactor to carry out hydrogenation reaction; reaction effluent is cooled and separated to obtain hydrogen-rich gas and liquid product; the hydrogenation reactor sequentially comprises four hydrogenation reaction zones, wherein, the first hydrogenation reaction zone is filled with hydrogenation protective agent, the second hydrogenation reaction zone is filled with hyrorefining catalyst (1)containing active metal cobalt-molybdenum, the third hydrogenation reaction zone is filled with the mixture of the hyrorefining catalyst (1) and hyrorefining catalyst (2), and the fourth hydrogenation reaction zone is filled with the hyrorefining catalyst (2) containing active metal nickel-tungsten. The invention carries out reasonable grading on catalyst of different systems, gives full play to the advantages of each catalyst in different desulphurizing states, improves whole catalyst activity by synergy of each catalyst, and can obtain ultra low sulfur diesel oil, sulfur content of which satisfies Euro IV standard under moderate operation condition.

The invention discloses an inferior diesel oil hydrodesulfurization method. Under the hydrofinishing condition, raw materials diesel oil and hydrogen are mixed and pass through four reaction zones in order; reaction products are cooled and enter a separation system so as to obtain a liquid product and a hydrogen-rich gas. A first catalyst is filled in a first reaction zone; a mixture of the first catalyst and a second catalyst are filled in a second reaction zone; the second catalyst is filled in a third reaction zone; and the first catalyst is filled in a fourth reaction zone, wherein the first catalyst is an Mo-Co catalyst and the second catalyst is a W-Mo-Ni catalyst or W-Ni catalyst. According to the invention, catalysts of different types and different hydrogenation activities are subjected to reasonable grading, and advantages of each catalyst at different desulphurization stages are fully performed. Through synergism of the catalysts, the whole catalyst activity is raised; and under a mild operational condition, ultra-low sulfur diesel oil, the sulfur content of which meets the European IV standard, can be obtained.

An improved method for desulfurizing a fuel stream such as a diesel stream is disclosed which includes generation of a sulfone oil, the desulfurization of the sulfone oil and the recycling of the resulting biphenyl-rich stream and ultra-low sulfur diesel streams. The method includes combining a thiophene-rich diesel stream with an oxidant to oxidize the thiophenes to sulfones to provide a sulfone-rich diesel stream. Sulfone oil is extracted from the sulfone-rich diesel stream to provide sulfone oil and a first low-sulfur diesel stream The low-sulfur diesel stream is recycled. The sulfone-rich oil stream is combined with an aqueous oxidant-containing stream, such as caustic stream, which oxidizes the sulfones to biphenyls and forms sulfite to provide a second low-sulfur diesel stream.

The invention is a method of purifying an ultralow sulfur diesel fuel which contains polycyclic aromatic color bodies. The method comprises contacting the ULSD fuel in the liquid phase with a coal-based activated carbon adsorbent having a surface area ranging from 800 to 1500 m2 / g and containing pores having pore size greater than 20 Å, and recovering a purified diesel product having a decreased color bodies content.

A process for preparing ultralow-sulfur diesel oil includes mixing refined low-sulfur diesel oil with phase-transfer catalyst and aqueous solution of hydrogen peroxide, stirring, reaction for converting the organic sulfide to sulfone and / or sulfoxide, recovering phase-transfer catalyst, removing excessive hydrogen peroxide, selectively removing sulfone and / or sulfoxide by polar solvent, and adsorption. The final sulfur content is lower than 10 ppm (even up to 0 ppm).

The invention relates to a production method for ultra-low sulfur diesel oil; wherein, after mixed with hydrogen, straight-run atmosphere 3rd side cut distillate and (or) diesel oil heavy distillate enter(s) a first hydrogenation reaction zone and reacts under the action of hydro-upgrading catalyst and hydrofining catalyst; after mixed with the reaction effluent of the first hydrogenation reaction zone, straight-run atmosphere 2nd side cut distillate and (or) diesel oil light distillate enter(s) a second hydrogenation reaction zone and reacts under the action of the hydrofining catalyst; the reaction effluent of the second hydrogenation reaction zone is cooled, separated and distilled to obtain naphtha fraction and diesel products. The method provided by the invention can treat the diesel distillate with high sulfur, high nitrogen and high final boiling point, and under mild operating conditions, obtain clear diesel products with low content of sulfur and polycyclic aromatic hydrocarbons as well as high cetane number; meanwhile, the product quality can reach the indexes of the IV European emission standard.

The invention discloses a hydrogenation technology for diesel, comprising the following steps: distilling a diesel raw material into light components and heavy components; under the hydrogenation refined condition, carrying out hydrorefining reaction on the heavy components in a first reaction region; mixing effluents at the first reaction region with the light components to enter a second reaction region for the hydrorefining reaction; and carrying out separation treatment on the effluents in the second reaction region. Compared with the prior art, by the technology in the invention, released reaction heat is effectively utilized in the hydrorefining process of the diesel raw material, a great amount of cold hydrogen is not used, and the negative influence of nitrogenous compounds and nuclei aromatics in the heavy components on deep desulfuration reaction of the diesel is overcome; and simultaneously, the technology is simple, energy consumption is reduced, and ultra low sulfur diesel products can be manufactured by using the technology.

A method of detecting the amount of sulfur compounds in fuels such as ultra low sulfur diesel (ULSD) fuels is provided in which a fuel sample is reacted with a solvent and an oxidizing agent to produce a reaction product which may be analyzed by visual observation and / or in combination with spectrophotometric or colorimetric analysis. The oxidizing agent may be selected from potassium permanganate, sodium dichromate, nitric acid, hydrogen peroxide, cumene hydroperoxide, and sodium hypochlorite, and may be used in combination with an acid.

The invention relates to a method for grading catalysts for hydrofining of inferior distillate oil. A hydrogenation reactor is divided into three sections of reaction regions sequentially from top to bottom, wherein a hydrogenating protective agent is filled in the first section of reaction region; a hydrofining agent A is filled in the second section of reaction region and is characterized in that the catalyst adopts Al2O3-TiO2-SiO2-ZrO2 quaternary composite oxide as a carrier, W-Mo-Ni ternary metal as an active metal component and P as an aid; and a hydrofining agent B is filled in the third section of reaction and is characterized in that the catalyst adopts Al2O3-SiO2-ZrO2 ternary composite oxide as a carrier, W-Mo-Ni ternary metal as an active metal component and P and F as aids. The method is used for grading different systems of catalysts reasonably, wherein due to combination of the hydrofining agent A with large pore volume, large specific surface area and high surface acid quantity and the ternary metal component with high activity, certain desulfuration and deep denitrogenation effects are achieved, and the influence of azacyclo compounds on the desulfurization activity of the catalyst in the next step is reduced; and due to the hydrofining agent B and the deep desulfurization performance of the catalyst, ultralow sulfur diesel oil with the sulfur content meeting the European IV standard is obtained finally.

The invention relates to a hydrogenation system for producing ultralow-sulfur diesel oil, and a method thereof. The system comprises a first-segment hydrogenation reaction zone a second-segment hydrogenation reaction zone; the first-segment hydrogenation reaction zone is an upflow fixed bed reactor; the second-segment hydrogenation reaction zone is an active hydrogenation catalyst layer filled in an upper portion of a thermal high stripping reactor; a reaction raw material enters from the bottom of the upflow fixed bed reactor, and a reaction product flows out through the top of the upflow fixed bed reactor and directly enters the thermal high stripping reactor from a position over the second-segment hydrogenation reaction zone; a liquid phase in the upflow fixed bed reactor is a continuous phase, and a gas phase in the upflow fixed bed reactor is a disperse phase; and stripped hydrogen is introduced to the thermal high stripping reactor from a position below the second-segment hydrogenation reaction zone, and the above first-segment hydrogenation reaction product has a countercurrent contact with the stripped hydrogen for a super-deep hydrodesulfurization reaction and product stripping. The above finally-obtained reaction product is partially returned to an inlet of the first-segment hydrogenation reactor as circulation oil. The hydrogenation system for producing ultralow-sulfur diesel oil, and the method are economic and efficient.

Disclosed is a method for production of ultralow-sulfur diesel oil. Raw oil of diesel oil fraction enters a reactor from the top, make-up hydrogen and circulating hydrogen are mixed and then enter the reactor from the bottom, the raw oil of diesel oil fraction sequentially contacts a hydrofining catalyst I and a hydrofining catalyst II for reaction under the hydrofining reaction conditions, and the reaction products are separated and fractionated to obtain diesel oil product. The hydrofining catalyst I is a loaded hydrofining catalyst using nickel-molybdenum or nickel-molybdenum-tungsten as active metal component, and the hydrofining catalyst II is a bulk hydrofining catalyst. The invention can solve the problems of harsh operating conditions and low space velocity in prior art.

A method for determining the variations in the sulfur content of ultra-low sulfur diesel fuel when it is transported through a petroleum transportation system includes sampling fuels at various points during barge transport, pipeline transport and in terminaling operations. New procedures and special handling regiments are developed in view of how the sulfur content of ultra-low sulfur fuel may change when transported through the system in sequence and stored with other petroleum products.

The invention discloses a method for producing ultra-low-sulfur diesel in a long period. The method comprises the following steps: enabling a diesel raw material and hydrogen to contact a hydrofining catalyst I in a first reaction zone to implement a reaction, feeding a reaction effluent of the first reaction zone into a second reaction zone without separation, contacting a hydrofining catalyst II to implement a reaction, cooling an effluent of the second reaction zone, separating, and distilling, thereby obtaining a diesel product, wherein the content of sulfur of a liquid-phase effluent in the reaction effluent of the first reaction zone is 20-200mu g / g, and the content of nitrogen is 0-50mu g / g. By adopting the method, not only is a diesel fraction with high sulfur converted into a diesel product of which the sulfur content is less than 10mu g / g, but also the operation period of a device is effectively prolonged.

The invention relates to an ultra-low-sulfur diesel lubricating property improver and a preparation method thereof. The improver is a mixture of monoglyceride, fatty acid and low-molecular-weight alcohol. The improver has acid value being lower than 30.0mgKOH / g and a condensation point being lower than -1 DEG C. according to the preparation method, biodiesel co-product glycerin and low-molecular-weight alcohols serving as the raw materials have esterification reaction with the fatty acid in the presence of an ionic liquid catalyst to generate the mixture of monoglyceride, fatty acid and low-molecular-weight alcohols, namely the ultra-low-sulfur diesel lubricating property improver, wherein the addition of the improver relative to low-sulfur diesel is 50mu g / g, the temperature is 100-170 DEG C, the pressure is 0.1-0.2MPa and the time is 1-2 hours. The detailed preparation method refers to the specification. The low-sulfur diesel lubricating property improver has low acid value and high lubrication improvement property, can be directly used without use of antioxidants and cleaning agents; production cost is low, the production process is clean and the production flow is short.

This invention discloses a method for preparing low-sulfur diesel oil (sulfur content is less than 50 ppm). The method comprises: (1) stirring hydrogenated or unhydrogenated diesel oil and a mixture of Q+[MWxOy]- emulsion catalyst and H2O2 aqueous solution, and reacting under mild conditions to convert organic sulfide in diesel oil into sulfone and / or sulfoxide to obtain oxidized diesel oil; (2) separating the catalyst from oxidized diesel oil, and recovering; (3) washing oxidized diesel oil with distilled water, and removing most of sulfone and / or sulfoxide with a polar solvent to obtain low-sulfur diesel oil (sulfur content is less than 50 ppm).

A process for the autocatalytic production of organic hydroperoxides and ultra low sulfur diesel boiling range hydrocarbons is disclosed. The organic hydroperoxides react with sulfur compounds to produce sulfones, and the sulfones can be removed from the diesel boiling range hydrocarbons to provide ultra low sulfur diesel.

The invention discloses a grading method of catalyst of deep hydrodesulfurization of diesel oil, comprising the following steps: base oil and hydrogen are mixed, then the mixture is led into a hydrogenation reactor to carry out hydrogenation reaction; reaction effluent is cooled and separated to obtain hydrogen-rich gas and liquid product; the hydrogenation reactor sequentially comprises four hydrogenation reaction zones, wherein, the first hydrogenation reaction zone is filled with hydrogenation protective agent, the second hydrogenation reaction zone is filled with hyrorefining catalyst (1)containing active metal cobalt-molybdenum, the third hydrogenation reaction zone is filled with the mixture of the hyrorefining catalyst (1) and hyrorefining catalyst (2), and the fourth hydrogenation reaction zone is filled with the hyrorefining catalyst (2) containing active metal nickel-tungsten. The invention carries out reasonable grading on catalyst of different systems, gives full play to the advantages of each catalyst in different desulphurizing states, improves whole catalyst activity by synergy of each catalyst, and can obtain ultra low sulfur diesel oil, sulfur content of which satisfies Euro IV standard under moderate operation condition.

According to this invention, a Ni—Mo—W trimetallic catalyst supported on porous alumina is obtained that shows very high activity for hydrotreating (HDT) of gasoils, particularly deep hydrodesulfurization (HDS) and hydrodesnitrogenation (HDN) of straight run gasoil in conditions of moderate pressure.When the catalyst is applied to HDT of diesel, the NiMoW catalyst exhibits high catalytic activity. The content of sulfur and nitrogen in the resulting diesel can be reduced from 13,200 to 10 ppm and nitrogen from 360 ppm to less than 1 ppm, under moderate pressure, temperature and space-velocity (LHSV) similar to those of an industrial unit.The catalytic composition, of trimetallic type, is prepared from an alumina support of high surface area to which a solution containing a metal precursor of an element of group VIB is added, followed by other solution that contains one of the precursors of the active metallic phase, a solution containing another of the precursors of the active metallic phase from group VIB, a metal promoter of group VIII and an additive promoter of acidity from group VB, and finally another solution containing a metal of group VIB, a metal of Group VIII and an organic compound, the used route promotes the preferential formation of well dispersed structures of the used metals on the support of porous alumina, less refractory to sulfidation, with high stacking and short lengths of metal sulfides formed in the resulting hydrodesulfurization catalyst. In the formulation, at least a percentage, but not all the Mo is replaced by W, in a Mo / W molar ratio of 0.6 to 2.0.

The invention discloses a low-cost combined hydrofinishing method of oil products. The low-cost combined hydrofinishing method comprises following steps: firstly, hydrogen is mixed with a liquid phase material; the liquid phase material with dissolved hydrogen is delivered into a liquid phase hydrogenation reactor for reaction; an obtained material is delivered into a counter current reactor through the upper part of the counter current reactor, and is further reacted with a small amount of fresh hydrogen which is delivered into the counter current reactor through the bottom of the counter current reactor; and a part of an obtain liquid product is recycled into the liquid phase hydrogenation reactor, and the rest is taken as a hydrogenation products. Compared with existing liquid phase hydrogenation method, the low-cost combined hydrofinishing method is capable of preparing ultra-low-sulfur diesel oil with sulfur content less than 10<mu>g / g directly, and reducing equipment investment and operation cost greatly; and operation is flexible, and raw material adaptability is high.

The invention provides a hydrotreating method for producing low-sulphur and ultra-low sulphur diesel oil, which comprises the following steps of: subjecting raw oil into pre-hydrogenation reaction in the first reaction region, then fractionating the diesel oil into a light fraction and a heavy fraction after implementing pre-hydrogenation, and then absorbing or extracting the heavy fraction to remove the organic nitrogen-containing compound which has an inhibition effect to deep desulfurization; infusing the heavy fraction into the second reaction region to implement deep hydrodesulfurization after removing the organic nitrogen-containing compound; and mixing the light fraction and the heavy fraction to obtain producing low-sulphur or ultra-low sulphur diesel oil. Compared with conventional refining process of diesel oil, the hydrotreating method for producing low-sulphur and ultra-low sulphur diesel oil provided by the invention has the advantages that the purpose for deep or ultra-deep hydrodesulfurization of diesel oil can be realized in the condition that the whole operation conditions are relatively mild due to the point that the negative factor which can influence the deep hydrodesulfurization of diesel oil is removed, and the hydrogen consumption of the method is relatively low.

The invention disclosed an oxygenized desulphuring method of hydrogenated diesel oil distillate. The invention only treats the heavy distillate rather than the light distillate. The processing procedure comprises the following steps: dividing the hydrogenated diesel oil into light distillate and heavy distillate; adding the oxidant (the mole ratio of oxidant to sulphur is 2-10); adding the acid assistant (the mole ratio of the oxidant to the acid assistant is 0.5-3) to oxidize the sulphide into the sulfone; using extracting separation or adsorbing separation to remove the sulfone or sulfoxide substances in the diesel oil; mixing the heavy distillate with the light distillate to get the diesel oil with supra-low content of sulphur. The invention is especially applicable to the hydrogenated diesel oil distillate which contains less than 500500 mug / g sulphur. It can remove the dibenzothiophene substance effectively, the sulphur content of the product is less than 1010 mug / g while the oil vecovery rate is 5wt%-15wt% higher than the regular ways without fractional distillating process.

A catalyst for ultra-deep desulfurization of diesel via oxidative distillation is an amphiphilic oxidative catalyst, which is expressed as Qm[XMnOq], wherein 1≦m≦12; 9≦n≦18; 34≦q≦62; Q is a quaternary ammonium cation; X is P, Si, As or B; and M is Mo) or W. A desulfurization method comprises a) mixing well a diesel, the amphiphilic catalyst, and hydrogen peroxide, reacting for 10-300 minutes at ambient temperature and normal pressure, transforming the sulfur-containing compounds in the diesel into sulfone to obtain an oxidized diesel; b) distilling the oxidized diesel obtained in step a) under reduced pressure to obtain the ultra-low sulfur diesel having a sulfur content of less than 10 ppm; and c) separating and recovering the catalyst and sulfone.

A hydro-processing method for producing ultra-low sulfur diesel comprises the following steps: completely dissolving the hydrogen I in diesel fraction raw oil to enter into a first hydro-processing reaction zone to be contacted with hydro-processing catalyst under pure liquid phase; reacting under the temperature of 340 to 400 DEG C; mixing the effluent of the first hydro-processing reactor with the hydrogen II to enter into a second hydro-processing reaction zone to be contacted with the hydro-processing catalyst under the state of pure liquid phase or low hydrogen-oil ratio; reacting under the reaction temperature of 240-320 DEG C, and cooling and separating the effluent of the second hydro-processing reaction zone to obtain diesel product. The method of the invention can be used for translating the diesel fraction with high sulfur content into ultra-low sulfur diesel product with good color, wherein the sulfur content can meet the Euro IV and Euro V discharge standard requirement and simultaneously, the chromaticity is less than 0.5.

A method for determining the variations in the sulfur content of ultra-low sulfur diesel fuel when it is transported through a petroleum transportation system includes sampling fuels at various points during barge transport, pipeline transport and in terminaling operations. New procedures and special handling regiments are developed in view of how the sulfur content of ultra-low sulfur fuel may change when transported through the system in sequence and stored with other petroleum products.

The invention relates to a diesel oil deep hydrodesulfurization method, which comprises that diesel oil raw material oil and hydrogen enter a reactor and are subjected to a hydrogenation reaction under the effect of a hydrogenation catalyst I, the reactor effluent is subjected to heat exchange, the obtained material enters a hot high pressure separator, a hydrogenation catalyst II is filled on the middle portion of the hot high pressure separator, and the liquid-phase stream separated by the hot high pressure separator is subjected to cooling and fractionation to obtain the hydrogenation gasoline and the hydrogenation diesel oil. According to the present invention, the straight-run diesel oil or poor-quality secondary processing diesel oil can be treated, the ultra-low sulfur diesel oil with the sulfur content of less than 10 ppm can be produced, the hydrogenation decolorization reaction can be separately completed without the separate hydrogenation decolorization reactor, and the product ASTMD1500 chrominance is less than 1.0.