DE102008022378A1 - Sulfur-free diesel fuel and high-octane petroleum manufacturing method, involves mixing discharge flows for providing mixing flow, and separating mixing flow in fractionation zone to produce diesel fuel and high-octane petroleum flows - Google Patents

Abstract

The method involves reacting a distillate hydrocarbon-material component and a hydrogen-rich, gaseous auxiliary flow in a hydrodesulfurization-reaction zone (5) having a desulfurization-catalytic converter to generate a hydrodesulfurization-reaction zone-discharge flow. A high-aromatic hydrocarbon-material component is reacted in a hydro cracking zone (17) to generate a hydro cracking zone-discharge flow. The discharge flows are mixed to provide a mixing flow, and the mixing flow is separated in a fractionation zone (22) to produce sulfur-free diesel fuel and high-octane petroleum flows.

Description

BACKGROUND OF THE INVENTION

The The present invention relates to a process for the preparation low-sulfur diesel fuel and high-octane petrol. In particular, the invention is an integrated method for Hydrodesulfurization (HDS) of middle distillate hydrocarbon streams and hydrocracking of high aromatic hydrocarbon streams.

Petroleum refining companies produce desirable products, such as turbine fuel, diesel fuel and middle distillates, as well as naphtha and heavy fuel, by hydrocracking a hydrocarbon feedstock, for example from crude oil is derived. Feedstock, in most cases are subjected to hydrocracking, are gas oils, the be recovered by distillation from crude oil. refining companies subject middle distillate hydrocarbon streams still Hydrodesulfurization (HDS). Although a wide variety of Process Flow Schemes, Operating Conditions and Catalysts have been used in economic activities, there is still a need for new hydroprocessing processes, lower costs, more valuable product yields and improved Operability result.

EPIPHANY

US 4,943,366 (Fischer et al.) Discloses a hydrocracking process for the conversion of highly aromatic, substantially dealkylated feedstock to high octane naphtha.

SUMMARY OF THE INVENTION

The The present invention is an integrated method for the production of low sulfur diesel fuel and high octane Naphtha. The method of the present invention uses a Middle distillate hydrocarbon stream and a highly aromatic Hydrocarbon stream. The middle distillate hydrocarbon feedstock is added with fresh hydrogenation in a hydrodesulfurization reaction zone Reaction brought, and the highly aromatic hydrocarbon stream is reacted in a hydrocracking zone with hydrogen chloride brought. The resulting discharges from the two zones are in a common high-pressure vapor liquid separator introduced to a hydrogen-rich recycle gas and a liquid stream, the desulphurised diesel fuel and high-octane petroleum spirit contains, which are then deposited subsequently become.

Of the Use of additional hydrogen as a source of hydrogen for the hydrodesulfurization reaction zone minimizes the load of the recycle compressor, and the use of common deposition and fractionation zones brings the benefits of lower capital outlay and lesser Operating cost.

Other Embodiments of the present invention include more details, such as detailed descriptions feedstocks, hydrodesulfurization catalysts, the hydrocracking catalysts and preferred operating conditions, which in the following discussion of these individual aspects of the Invention disclosed.

BRIEF DESCRIPTION OF THE DRAWING

The Drawing is a simplified process flow diagram of a preferred embodiment of the present invention. The drawing is intended to schematically illustrate the present invention, but do not restrict them.

DETAILED DESCRIPTION THE INVENTION

The present invention is an integrated process for the hydrodesulfurization of middle distillate hydrocarbon streams and the hydrocracking of high aromatic hydrocarbon streams. Preferred feedstocks for the hydrodesulphurization reaction zone include distillate hydrocarbons having a boiling point of above 149 ° C (300 ° F), and more particularly having a boiling temperature in the range of 149 ° C (300 ° F) to 399 ° C (750 ° F). , Distillate hydrocarbon feed is recovered in most cases by distillation from crude oil. However, distillate hydrocarbons can be made from any useful or convenient sources, such as tar sands extract and gas to liquid be used. Furthermore, distillate hydrocarbon feedstocks may contain from 0.1 to 4 weight percent sulfur.

The preferred high aromatic hydrocarbon feeds have a boiling point in the range of 149 ° C (300 ° F) to 343 ° C (650 ° F). Highly aromatic, essentially dealkylated hydrocarbons are formed during the catalytic Fluidized Cracking (FCC) of vacuum gas oils for production of hydrocarbons in the boiling range of high octane naphtha produced. The FCC is a thermally heavy process that works without the presence of added hydrogen is operated to carbon to discard coke and to produce residual fractions. While of the catalytic cracking disproportionates the feedstock with high molecular weight relative to relatively hydrogen-rich Light liquids and aromatic heavier distillates and residues with hydrogen deficiency. The catalytic cracking in the absence of hydrogen does not produce any essential hydrodesulfurization ready, and the nitrogen content The feedstock is also not selectively discarded with the coke. The sulfur and the nitrogen therefore accumulate in the heavier Cracked products and produce substantial amounts of highly aromatic middle distillates and heavy distillates with hydrogen deficiency and with high sulfur and nitrogen contents. The return of this Liquids in the catalytic cracking unit is not interesting or appealing solution. A typical easy one Circulatory oil (LCO) from a fluid catalytic cracking contains three percent by weight sulfur, 700 wppm (ppm by weight) Nitrogen and more than 80 percent by volume of aromatic hydrocarbons. Current market requirements require that refractory Product streams, such as light cycle oil, particularly difficult to sell as economically salable products are.

In one embodiment of the present invention, a highly aromatic and substantially dealkylated hydrocarbon feed with hydrogen deficiency is introduced into a hydrocracking zone. The hydrocracking zone may contain at least one bed of the same catalyst or different catalysts. In one embodiment, the preferred hydrocracking catalysts utilize amorphous bases or lower zeolite bases in combination with at least one Group VIII or Group VIB metal hydrogenation component. In another embodiment, the hydrocracking zone contains a catalyst, generally comprising any crystalline zeolite cracking base upon which a small portion of a Group VIII metal hydrogenation component is deposited. Additional hydrogenation components can be selected from Group VIB for incorporation into the zeolite base. The zeolite cracking bases are sometimes referred to in the art as molecular sieves and are usually silica, alumina, and at least one exchangeable cation, such as sodium, magnesium, calcium, rare earth metals, etc. They are further characterized by relatively uniform diameter crystal pores four and 14 angstroms (10 ^-10 meters). Preferably zeolites are used with a molar ratio of silica / alumina between three and 12. Suitable zeolites found in nature are, for example, mordenite, stilbite, heulandite, ferrierite, dachiardite, chabazite, erionite and faujasite. Suitable synthetic zeolites include the crystal types B, X, Y and L, such as synthetic faujasite and modernite. The preferred zeolites are those having a crystal pore diameter between eight and 12 angstroms (10 ^-10 meters) with the silica / alumina molar ratio being from four to six. A most important example of a zeolite falling within the preferred group is a synthetic Y molecular sieve.

The naturally occurring zeolites are usually in a sodium form, an alkaline earth metal form or in mixed forms. The synthetic zeolites are almost always prepared first in the sodium form. In any event, for use as a cracking base, almost all of the original zeolitic monovalent metals are preferably internally exchanged with a polyvalent metal and / or with an ammonium salt, followed by heating to decompose the ammonium ions associated with the zeolite, replacing hydrogen ions and / or exchange sites left over, which have actually been cationized by further dehydration. Hydrogen or "decationized" Y zeolites of this type are discussed in more detail US 3,130,006 described.

Mixed polyvalent metal-hydrogen zeolites can be prepared by first exchanging them with ammonium salt ions, then partially exchanging them with a polyvalent metal salt and then calcining them. In some cases, such as in the case of synthetic mordenite, the hydrogen forms can be prepared by direct acid treatment of the alkaline metal zeolites. The preferred cracking bases are those of at least 10 percent concentration, and preferably 20 percent concentration, with a metal cation deficiency based on the original ion exchange capacity. A particularly desirable and stable class of zeolites are those in which at least 20 percent of the ion exchange capacity is met by hydrogen ions the.

The in the preferred hydrocracking catalysts of the present invention Invention are active metals used as hydrogenation components those of group VIII, such as iron, cobalt, nickel, Ruthenium, rhodium, palladium, osmium, iridium and platinum. additionally These metals can also be used in other accelerators Connection with the same can be used, including including the metals of group VIB, such as molybdenum and tungsten. The amount of hydrogenation metal in the catalyst can vary in a wide range. Roughly speaking, any Amount used between 0.05 weight percent and 30 weight percent become. In the case of precious metals normally 0.05 to two weight percent preferred. The preferred method of incorporation the hydrogenation metal is contacting the zeolite base material with an aqueous solution of a suitable compound of the desired metal, the metal being in a cationic Form is present. After the addition of the selected hydrogenation metal or the selected hydrogenation metals will be the resulting Catalyst powder then filtered, dried, optionally under Addition of lubricants, binders or the like pelettiert and at air temperatures of, for example, 371 ° C to 648 ° C (700 ° F to 1200 ° F) calcined to the catalyst activate and break down ammonium ions. Alternatively, it can the zeolite component is first peletted, followed by the Addition of the hydrogenation component and activation by calcining. The The above mentioned catalysts can be used undiluted Form are used, or the pulverized zeolite catalyst may interact with other relatively less active catalysts, diluents or binders, such as alumina, silica gel, Silica-alumina gels, activated clays and the like mixed in proportions between five and 90 percent by weight and be relegated. These diluents can can be used unchanged or they can a minor proportion of an added hydrogenation metal, such as a metal of group VIB and / or the group III, included.

Additive metal promoted hydrocracking catalysts may also be employed in the process of the present invention, such as aluminophosphate molecular sieves, crystalline chromosilicates, and other crystalline silicates. Crystalline chromosilicates are described in more detail US 4,363,718 (Log) described.

Hydrocracking of the hydrocarbonaceous feedstock in contact with a hydrocracking catalyst is conducted in the presence of hydrogen, and preferably under hydrocracking reactor conditions having a temperature of 260 ° C (500 ° F) to 426 ° C (800 ° F), a pressure of 7.0 MPa (1,000 psig) to 10.5 MPa (1500 psig), a liquid hourly space velocity (LHSV) of 0.1 to 30 h ^-1, and a hydrogen recycle rate of 2,000 (337 standard cubic meters / m ³ ) to 25,000 (4,200 standard cubic meters / m ³ ) standard cubic feet per barrel.

Of the The resulting effluent from the hydrocracking zone is preferably contacted with an aqueous stream to any Dissolve ammonium salts, and then partially condensed and then into a high pressure vapor-liquid separator which is operated at a pressure substantially equal to that of the hydrocracking zone and at a temperature in the range of 38 ° C (100 ° F) to 71 ° C (160 ° F). An aqueous stream is removed from the vapor liquid separator recovered. A hydrogen-rich gaseous Current is withdrawn from the vapor liquid separator, at least the largest part of the hydrogen and preferably all of the hydrogen entering the hydrocracking zone is initiated to provide.

In one embodiment of the present invention, a distillate hydrocarbon having a boiling point greater than 149 ° C (300 ° F) is introduced into a desulfurization reaction zone along with a hydrogen-rich makeup stream under desulfurization reaction conditions. Preferred desulfurization reaction conditions include a temperature of 260 ° C (500 ° F) to 426 ° C (800 ° F), a pressure of 7.0 MPa (1,000 psig) to 10.5 MPa (1500 psig), and a liquid phase. Hourly space velocity from 0.1 h ^-1 to 10 h ^-1 .

Suitable desulfurization catalysts for use in the present invention are any known desulfurization catalysts and include those consisting of at least one Group VIII metal, preferably iron, cobalt and nickel, more preferably cobalt and / or nickel, and at least one metal of the group VI, preferably molybdenum and tungsten, on a large-area support material, preferably alumina exist. Other suitable desulfurization catalysts include zeolitic catalysts and noble metal catalysts wherein the noble metal is selected from palladium and platinum. Within the scope of the present invention, at least one type of desulfurization catalyst may be employed in the same reaction vessel. The metal of Group VIII is typi in an amount of from 2 to 20% by weight, preferably from 4 to 12% by weight. The Group VI metal is typically present in an amount of from one to 25 percent by weight, preferably from two to 25 percent by weight.

Of the resulting effluent from the desulfurization reaction zone is with an aqueous stream in contact and partially condensed and then in the already described above High-pressure vapor liquid separator initiated.

fresh Additional hydrogen is added directly to the desulfurization reaction zone introduced to supply high purity hydrogen to the To maximize the activity of the desulfurization catalyst. In a preferred embodiment, at least a major part of the hydrogen-rich recycle gas, recovered in the high-pressure vapor-liquid separator is returned to the hydrocracking zone, and more preferably, substantially the entire hydrogen-rich recycle gas returned to the hydrocracking zone.

DETAILED DESCRIPTION THE DRAWING

In In the drawing, the method of the present invention by means of a simplified process flow diagram illustrates in the details, such as pumps, equipment, Heat exchange and heat recovery circuits, Compressors and similar aggregates have been omitted, since they are responsible for understanding the procedures involved are not significant. The use of the mentioned different aggregates is within the knowledge of one of ordinary skill in the art.

With reference to the drawing, distillate hydrocarbon feed is passed over the line 3 introduced into the process and mixed with a fresh stream of hydrogen passing through the line 1 is initiated. The resulting mixture is passed through the line 4 transported and in the hydrodesulfurization reaction zone 5 initiated. An emerging effluent from the hydrodesulfurization reaction zone 5 is over the wires 6 and 8th transported and into a high pressure cold separator 9 initiated. A hydrogen-rich gaseous stream is sent over the line 10 from the high-pressure cold separator 9 pulled off and into the compressor 11 initiated. A resulting compressed hydrogen-rich gaseous stream is passed through the conduits 12 and 14 transported and mixed with a light cycle oil feed through the pipe 16 is fed, and the resulting mixture is passed through the line 2 transported and into the hydrocracking zone 17 initiated. An emerging effluent from the hydrocracking zone 17 gets through the wires 7 and 8th transported and into the high pressure cold separator 9 initiated. Another hydrogen-rich gaseous stream is through the line 15 into the hydrodesulfurization reaction zone 5 initiated. Yet another hydrogen-rich gaseous stream is passing through the conduit 13 into the hydrocracking zone 17 initiated to provide quenching. A hydrocarbon-containing liquid stream is passed through the line 18 from the high-pressure cold separator 9 withdrawn and into the low pressure relaxation drum 19 initiated. A gaseous stream containing hydrogen and low-boiling gaseous hydrocarbons passes through the conduit 20 from the low pressure relaxation drum 19 deducted and recovered. A liquid hydrocarbon-containing stream is passed over the line 21 from the low pressure relaxation drum 19 withdrawn and into the fractionation zone 22 initiated. A normally gaseous hydrocarbon-containing stream is passed over the line 23 withdrawn from the fractionation zone and recycled. A high-octane Rohbenzinstrom is over the line 24 from the fractionation zone 22 deducted and recovered. The high octane crude gasoline stream may be removed from the fractionation zone in any convenient manner 22 are drawn off and is preferably a side fraction, as shown. A low sulfur diesel fuel stream is sent over the line 25 from the fractionation zone 22 deducted and recovered.

The Method of the present invention will be illustrated by the following Embodiment further illustrated. The Illustrative embodiment, however, the method not excessive in the present invention restrict, but the benefits of the above Further illustrate exemplary embodiment. The following Data did not come out of fact of the present invention won, but are for the expected execution of the invention as being prospective and adequately illustrative consider.

ILLUSTRATIVE EMBODIMENT

A blend of distillate diesel fuel and light coker gas oil (LCGO) in an amount of 4,372 m ³ / day (27,500 barrels per day) and having the properties given in Table 1 is compounded with a high purity additional hydrogen stream into a hydrodesulfurization reaction zone operating under hydrodesulfurization reaction conditions summarized and presented in Table 2.

A stream of light FCC cycle oil (LCO) in an amount of 3,657 m ³ / day (23,000 barrels per day) having the properties shown in Table 1 is introduced into a hydrocracking zone prepared under hydrocracking conditions, summarized in Table 2 and be operated.

The resulting effluent from the hydrodesulphurization reaction zone and hydrocracking zone is cooled, partially condensed and passed into a cold high pressure steam liquid separator operating at a pressure of 9.7 MPa (1400 psig) and at a temperature of 43 ° C (110 ° C) F) to produce a hydrogen-rich recycle gas stream and a liquid hydrocarbon-containing stream. The hydrogen rich recycle gas stream is recycled to the hydrocracking zone and the liquid hydrocarbonaceous stream is fractionated to produce a high octane crude gasoline stream having a boiling point in the range of 88 ° C (185 ° F) to 193 ° C (380 ° F) in an amount of 5,500m ³ / day (34,500 barrels per day) and with a sulfur content of <10 ppm and an octane rating of 46. TABLE 1 - ANALYSIS OF THE APPLICATION MATERIAL Diesel / LCGO Light cycle oil relativ density 0.87 0.96 Total sulfur, 2 1 Weight percent total nitrogen, ppm weight distillation ° C (° F) 725 900 Initial boiling point (IBP) 146 (295) 215 (420) 10% 222 (432) 263 (506) 50% 278 (543) 304 (580) 90% 336 (638) 349 (660) EP 390 (735) 371 (700) TABLE 2 - OPERATING CONDITIONS hydrodesulfurization hydrocracking Pressure, MPa (psig) 9.7 (1.400) 9.7 (1,400) Temperature, ° C (° F) 371 (700) 3 (700)

The above description, the drawing and the illustrative Embodiment clearly illustrate the advantages of the process of the present invention and the benefits of the application of the same can be derived.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• US 4943366 [0003]
• - US 3130006 [0011]
• US 4363718 [0014]

Claims (10)

Integrated manufacturing process low-sulfur diesel fuel and high-octane petroleum gas, the method comprising: a) reacting a distillate hydrocarbon feedstock, that has a boiling range greater than 149 ° C (300 ° F) has, and a hydrogen-rich, gaseous additional stream in a hydrodesulfurization reaction zone, the desulfurization catalyst contains a hydrodesulfurization reaction zone effluent stream, containing hydrocarbons that produce a reduced Having sulfur concentration; b) reacting a highly aromatic, essentially dealkylated hydrocarbon feedstock in a hydrocracking zone containing hydrocracking catalyst, to produce a hydrocracking zone effluent, the monocyclic produce aromatic compounds boiling in the naphtha range; c) Mixing the hydrodesulfurization reaction zone effluent stream and the hydrocracking zone effluent stream to produce a resultant To provide mixing flow, and d) depositing the resulting Mixing stream from step c) to a hydrogen-rich, gaseous stream, a low-sulfur diesel fuel stream and to produce a high octane crude gasoline stream. The method of claim 1, wherein the resulting Hydrodesulfurization reaction zone effluent mixture stream and the hydrocracking zone effluent stream into a high pressure vapor liquid separator is introduced to the hydrogen-rich, gaseous Electricity and an admixture containing the liquid hydrocarbons from the hydrodesulfurization reaction zone effluent and the Hydrokrackungszonen drain stream contains to produce. The method of claim 1, wherein the largest Part of the hydrogen-rich, gaseous stream from the Step d) returned to the hydrocracking zone wherein the hydrogen-rich gaseous stream is hydrogen from both the hydrodesulfurization zone effluent stream and out contains the hydrocracking zone effluent stream. Process according to claim 1, wherein the highly aromatic, Substantially dealkylated hydrocarbon feedstock hydrocarbons which is in the range of 149 ° C (300 ° F) boiling to 343 ° C (650 ° F). The process of claim 1, wherein the distillate hydrocarbon feedstock in the range of 149 ° C (300 ° F) to 399 ° C (750 ° F) boils and reduced hydrocarbons in the Has crude gasoline range. The process of claim 1 wherein the hydrodesulfurization reaction zone operated under conditions that maintain a pressure of 7.0 MPa (1,000 psig) to 10.5 MPa (1500 psig) and a temperature of 260 ° C (500 ° F). to 426 ° C (800 ° F). Process according to claim 1, wherein the highly aromatic, essentially dealkylated hydrocarbon feedstock lightweight Circulatory oil includes. The process of claim 1, wherein the hydrocracking zone operated under conditions that maintain a pressure of 7.0 MPa (1,000 psig) to 10.5 MPa (1500 psig) and a temperature of 260 ° C (500 ° F) to 426 ° C (800 ° F). The method of claim 1, wherein step (d) is carried out in at least one fractionation zone, the high octane crude gasoline stream being from the hydrocarbonaceous Content of admixed hydrodesulfurization reaction zone effluent and the hydrocracking zone effluent stream is separated. The method of claim 1, wherein substantially the entire hydrogen-rich gaseous stream from the Step (d) returned to the hydrocracking zone becomes.