CN104093821A - Integrated Hydrotreating And Steam Pyrolysis Process Including Hydrogen Redistribution For Direct Processing Of A Crude Oil - Google Patents

Abstract

A process is provided that is directed to a steam pyrolysis zone integrated with a hydroprocessing zone including hydrogen redistribution to permit direct processing of crude oil feedstocks to produce petrochemicals including olefins and aromatics. The integrated hydrotreating and steam pyrolysis process for the direct processing of a crude oil to produce olefinic and aromatic petrochemicals process comprises separating the crude oil into light components and heavy components; charging the heavy components and hydrogen to a hydroprocessing zone operating under conditions effective to produce a hydroprocessed effluent having a reduced content of contaminants, an increased paraffinicity, reduced Bureau of Mines Correlation Index, and an increased American Petroleum Institute gravity; charging the hydroprocessed effluent and steam to a convection section of a steam pyrolysis zone; d. heating the mixture from the convection section of a steam pyrolysis zone and passing it to a vapor- liquid separation section; removing from the steam pyrolysis zone a residual portion from the vapor-liquid separation section; charging light components from the initial separation step, a light portion from the vapor-liquid separation section, and steam to a pyrolysis section of the steam pyrolysis zone; recovering a mixed product stream from the steam pyrolysis zone; separating the mixed product stream; purifying hydrogen recovered from the mixed product stream and recycling it to the hydroprocessing zone; and recovering olefins and aromatics from the separated mixed product stream.

Description

For directly processing the hydrotreatment that comprises the integration that hydrogen distributes again and the water vapour method for pyrolysis of crude oil

Related application

The application requires the rights and interests of the U.S. Provisional Patent Application submitted on January 27th, 2012 number 61/591,814, and the disclosure of described application by reference integral body is incorporated to herein.

Background of invention

Invention field

The present invention relates to a kind of for directly processing crude oil to produce petroleum chemicals as the hydrotreatment of the integration of alkene and aromatics and water vapour method for pyrolysis.

Description of Related Art

Light alkene (that is, ethene, propylene, butylene and divinyl) and aromatics (that is, benzene, toluene and dimethylbenzene) are widely used basic intermediate in petroleum chemistry and chemical industry.For conventionally in the situation that there is water vapour and be used to form the method for the main Types of these materials in the situation that not there is not oxygen in thermo-cracking or water vapour pyrolysis.Raw material for water vapour pyrolysis can comprise that petroleum gas and overhead product are as petroleum naphtha, kerosene and gas oil.The availability of these raw materials normally limited and need the method steps expensive and energy-intensive in crude oil refineries.

Used heavy hydrocarbon to be studied as the raw material of water vapour pyrolysis reactor.Main drawback in conventional heavy hydrocarbon pyrolysis operations is that coke forms.For example, for the steam cracking method of heavy liquid hydrocarbon, be disclosed in U.S. Patent number 4,217, in 204, wherein the spray of fused salt be incorporated in steam cracking reaction zone and form to attempt minimizing coke.In use, have in the example of Arabian light of Conradson carbon value of 3.1 % by weight, cracking apparatus can be in the situation that there is fused salt ongoing operation 624 hours.In not adding the comparison example of fused salt, steam cracking reactor only after 5 hours due to reactor in the formation of coke become and block and can not operate.

In addition, use heavy hydrocarbon to be different from distributing those that use light hydrocarbon raw material as the alkene of the raw material of water vapour pyrolysis reactor and the productive rate of aromatics.Heavy hydrocarbon has the aromatic content higher than light hydrocarbon, as indicated in U.S. mineral bureau correlation index (BMCI) by higher.BMCI be raw material aromaticity tolerance and be calculated as follows:

BMCI＝87552/VAPB+473.5*(sp.gr.)-456.8 (1)

Wherein:

VAPB=is in the volume average boiling point of rankine degree (degrees Rankine), and

The proportion of sp.gr.=raw material.

Along with BMCI reduces, ethylene yield expection increases.Therefore, for water vapour pyrolysis, highly paraffinic or low aromatics charging are normally preferred, thereby obtain the required alkene of higher yields and avoid higher unwanted product and the coke in reactor coil pipe section to form.

Absolute coke in steam cracking device forms speed by people such as Cai, " Coke Formation in Steam Crackers for Ethylene Production, " Chem.Eng. & Proc., the 41st volume, (2002), 199-214 reports.In general, definitely coke formation speed is that wherein alkene represents heavy olefins according to the incremental order of alkene > aromatics > paraffinic hydrocarbons.

For can be in response to the demand to the growth of these petroleum chemicals, can be as attractive for the producer in crude oil with the charging of other type of relatively large acquisition.Use crude oil feeding in the production of these petroleum chemicals, to occur the possibility of bottleneck by minimizing or eliminate refinery.

Although water vapour method for pyrolysis well develops and is suitable for its predetermined object, the selection of raw material is always very limited.

Summary of the invention

System and method herein provides a kind of and comprises the water vapour pyrolysis zone of the hydrogenation processing district integration that hydrogen distributes again to allow directly processing crude oil material to produce petroleum chemicals, comprises alkene and aromatics.

For directly processing crude oil, to produce the hydrotreatment of olefinic and the integration of aromatic base crude oil chemical products, comprise with water vapour method for pyrolysis: described crude separation is become to light component and heavy component; Described heavy component and hydrogen charging are extremely being effective in to the hydrogenation processing district operating under the condition of the effluent that produces hydrogenation processing, and the effluent of described hydrogenation processing has the pollutant load of reduction, the U.S. mineral bureau correlation index of the paraffinicity of increase, reduction and American Petroleum Institute's proportion of increase; Effluent and the water vapour of described hydrogenation processing are feeded to the convection zone of water vapour pyrolysis zone; D. heat the described mixture from the described convection zone of water vapour pyrolysis zone, and it is passed to steam-liquid separation section; From described water vapour pyrolysis zone, remove the nubbin from described steam-liquid separation section; By the light component from described initial process step, from lightweight part and the water vapour of described steam-liquid separation section, feed to the pyrolysis section of described water vapour pyrolysis zone; From described water vapour pyrolysis zone, reclaim the product stream mixing; The product stream of separated described mixing; The hydrogen that purifying reclaims from the product stream of described mixing, and it is recycled to described hydrogenation processing district; And flow back to receipts alkene and aromatics from the mix products of described separation.

As used herein, term " crude oil " should be understood to include from the whole crude in routine source, experience some pretreated crude oil.Term crude oil also will be understood to include the crude oil that stands water-separating of oil and/or gas-separating of oil and/or desalination and/or stabilization.

The other side of method of the present invention, embodiment and advantage are discussing in detail below.In addition, should understand aforementioned information and following detailed description is all only the illustrative example of various aspects and embodiment, and aims to provide for understanding the character of feature required for protection and embodiment and the general survey of characteristic or framework.Accompanying drawing is illustrative and is provided to further understand different aspect and the embodiment of method of the present invention.

Accompanying drawing summary

The present invention will be following and be explained in further detail with reference to accompanying drawing, wherein:

Fig. 1 is the method flow diagram of the embodiment of integration method described herein; And

Fig. 2 A to Fig. 2 C is the exemplary illustration carrying out according to skeleton view, vertical view and the side-view of the steam-liquid separating appts using in some embodiment of the water vapour pyrolysis unit in integration method described herein.

Detailed Description Of The Invention

Have the hydrogenation processing of the integration that hydrogen distributes again and the method flow diagram of water vapour method for pyrolysis and system shown in Figure 1 comprising.In the overall system of described integration, comprise initial charge disengaging zone 20, selective catalytic hydrogenation processing district, water vapour pyrolysis zone 30 and product separation district.

In general, by crude oil feeding flash distillation, lighter fraction is (within the scope of the hydrogen that boiling point is easy to discharge at the hydrocarbon that contains the minimum further cracking of requirement and containing whereby, for example, up to approximately 185 ℃) be directly passed to water vapour pyrolysis zone, and necessary cut only, has the cut that is less than predetermined hydrogen richness and carries out hydrogenation processing.This is favourable, because it provides the hydrogen dividing potential drop of increase in hydrogenation processing reactor, thereby via the efficiency of saturated raising hydrogen transference.This will reduce hydrogen solution loss and H ₂consume.The hydrogen that is easy to discharge containing in crude oil feeding distributes to maximize the productive rate as the product of ethene again.Distributing again of hydrogen allows the generation of the overall reduction of heavy product and the increase of light olefin.

The first disengaging zone 20 comprises for receiving the entrance of feedstream 1, for discharging the outlet of light ends 22, and for discharging the outlet of heavy ends 226.Disengaging zone 20 can be single-stage tripping device, as the flash separator of cut point within the scope of approximately 150 ℃ to approximately 260 ℃.In certain embodiments, light ends 22 can be naphtha fraction.Table 1 illustrates the hydrogen richness based on different cut points.

In other embodiments, disengaging zone 20 comprises other tripping device or consisting essentially of (that is, the operating in the situation that not there is not flash zone) of eddy flow phase-separating device or the physics based on steam and liquid or mechanical separation.An example of steam-liquid separating appts by and with reference to Fig. 2 A to Fig. 2 C, describe.The similar arrangement of steam-liquid separating appts is also described in U.S. Patent Publication number 2011/0247500, and described patent by reference integral body is incorporated to herein.In described disengaging zone, comprise in the tripping device or consisting essentially of embodiment of physics based on steam and liquid or mechanical separation, the fluid velocity of the material that cut point can be based on gasification temperature and access to plant is adjusted

Table 1

The boiling point of light ends (℃)	Hydrogen richness (%)
		150	15.22
180	14.88
		200	14.73
260	14.34

Hydrogenation processing district comprises the hydrogenation processing reaction zone 4 with entrance, and described entrance is for receiving light fractions 21 and the mixture of hydrogen 2 from the recirculation of water vapour pyrolysis product stream and hydrogen make-up where necessary.Hydrogenation processing reaction zone 4 further comprises for discharging the outlet of the effluent 5 of hydrogenation processing.

From the reactor effluent 5 of described one or more hydrogenation processing reactors, in heat exchanger (not shown), carry out cooling and deliver to high-pressure separator 6.Separator headpiece 7 cleans in amine unit 12 and the resulting gas stream 13 that is rich in hydrogen is passed to recycle compressor 14 to be used as recycle gas 15 in described hydrogenation processing reactor.The bottoms 8 of liquid form haply that is from high-pressure separator 6 is carried out cooling and is introduced into low pressure cold separator 9, in bottoms described in described low pressure cold separator, is separated into gas stream and liquid stream 10.Gas from low pressure cold separator comprises hydrogen, H ₂s, NH ₃and any light hydrocarbon is as C ₁-C ₄hydrocarbon.Conventionally these gases are conveyed to further processing as burning processing (flare processing) or fuel gas processing.According to some embodiment herein, by comprising hydrogen, H ₂s, NH ₃and any light hydrocarbon is as C ₁-C ₄water vapour gas stream 11 and the steam cracking device product 44 of hydrocarbon combine to reclaim hydrogen.All or part of charging as water vapour pyrolysis zone 30 of liquid stream 10.

Water vapour pyrolysis zone 30 comprises convection zone 32 and pyrolysis section 34 generally, and described pyrolysis section can operate based on water vapour pyrolysis unit known in the art, in the situation that there is water vapour by thermo-cracking feed charge to described convection zone.In addition, in some optional embodiment as described herein (as indicated with dotted line in Fig. 1), between steam-liquid separation section 36 sections of being included in 32 and sections 34.Steam-liquid separation section 36 of passing through from the steam cracking charging of the heating of convection zone 32 can be physics based on steam and liquid or the tripping device of mechanical separation.

In one embodiment, steam-liquid separating appts by and with reference to Fig. 2 A to Fig. 2 C, describe.The similar arrangement of steam-liquid separating appts is also described in U.S. Patent Publication number 2011/0247500, and described patent by reference integral body is incorporated to herein.In this device, steam and liquid flow through with eddy flow geometrical shape, thus described device isothermal ground and operating under the low-down residence time.In general, steam is with circular pattern vortex with generation power, and heavier drop and liquid are waited to be hunted down and guided and for example passes through to liquid exit, as oil fuel 38,, it is added into pyrolysis fuel oil blend, and steam is guided through vapor outlet port as the charging 37 of pyrolysis section 34.Gasification temperature and fluid velocity are changed to adjust approximate temperature dividing point, for example compatible with residual fuel oil blend in certain embodiments, for example, at approximately 540 ℃.

Quench zone 40 comprise the entrance that is communicated with in fluid with the outlet of water vapour pyrolysis zone 30, for allow entrance that quenching solution 42 enters, for discharge quenching mixing product stream 44 outlet and for discharging the outlet of quenching solution 46.

In general, the product stream 44 of the middle mixing through quenching is converted to intermediate product stream 65 and hydrogen 62, and hydrogen carries out in the methods of the invention purifying and be used as recycle hydrogen air-flow 2 in hydrogenation processing reaction zone 4.Intermediate product stream 65 is fractionated into final product and resistates conventionally in disengaging zone 70, described disengaging zone can be one or more separating units, as a plurality of separation columns, comprises deethanizing column, depropanizing tower and debutanizing tower, for example as one of ordinary skill in the art known in.For example, applicable equipment describe is in " Ethylene, " Ullmann ' s Encyclopedia of Industrial Chemistry, the 12nd volume, the 531st page to 581 pages, specifically, in Figure 24, Figure 25 and Figure 26, described document is incorporated to herein by reference

In general, product separation district 70 comprises and product stream 65 and a plurality of product outlet 73 to 78 entrances that are communicated with in fluid, described a plurality of products export the outlet 78 that comprises for discharging methane, for discharge ethene outlet 77, for discharge propylene outlet 76, for discharge divinyl outlet 75, for discharge mixing butylene outlet 74 and for discharging the outlet 73 of pyrolysis gasoline.In addition, be provided for discharging the outlet of pyrolysis fuel oil 71.Optionally, combined and can be drawn out of as pyrolysis fuel oil blend 72 from oil fuel part 38 and the pyrolysis fuel oil 71 of steam-liquid separation section 36, for example, need to be carried out the further low sulphur fuel oil blend of processing in non-at-scene refinery.For example, although it should be noted that and show six products exports, can depend on that the arrangement of the separating unit that () adopts and output and distribution require and provide still less or more products outlet.

In the embodiment of method that adopts the arrangement shown in Fig. 1, crude oil material 1 is separated into light ends 22 and heavy ends 21 in the first disengaging zone 20.Light ends 22 is transported to the hot stage 36, walks around hydrogenation processing district, with the intermediate product with steam cracking, partly combines and produce mix products stream as described herein.

Heavy ends 21 mixes to form mix flow 3 with the hydrogen 2 and 15 of significant quantity.At temperature by mixture 3 in 300 ℃ to 450 ℃ scopes, feed to the entrance of selective hydrogenation processing reaction zone 4.In certain embodiments, hydrogenation processing reaction zone 4 comprises one or more unit operations of describing in U.S. Patent Publication as owned together number 2011/0083996 and PCT public announcement of a patent application WO2010/009077, WO2010/009082, WO2010/009089 and WO2009/073436, described patent all by reference integral body be incorporated to herein.For example, hydrogenation processing district can comprise one or more beds of the Hydrodemetalation catalyst that contains significant quantity, and one or more beds of the hydrogenation processing catalyst with Hydrodearomatization, hydrodenitrification, hydrogenating desulfurization and/or hydrocracking function that contains significant quantity.In other embodiments, hydrogenation processing reaction zone 4 comprises more than two catalyst beds.In other embodiments, hydrogenation processing reaction zone 4 comprises a plurality of reaction vessels of the catalyst bed that contains separately one or more (for example) difference in functionality.

Hydrogenation processing reaction zone 4 operates being effective under the parameter that makes crude oil material hydrodemetallation (HDM), Hydrodearomatization, hydrodenitrification, hydrogenating desulfurization and/or hydrocracking.In certain embodiments, use following condition to carry out hydrogenation processing: the service temperature in 300 ℃ to 450 ℃ scopes; Working pressure in 30 bar to 180 bar scopes; And at 0.1h ^-1to 10h ^-1liquid hourly space velocity in scope.

From the reactor effluent 5 of hydrogenation processing district 4, in interchanger (not shown), carry out cooling and deliver to cold high pressure or heat separator 6.Separator headpiece 7 cleans in amine unit 12 and the resulting gas stream 13 that is rich in hydrogen is passed to recycle compressor 14 to be used as recycle gas 15 in hydrogenation processing reaction zone 4.The bottom of the separator from high-pressure separator 6 thing 8 that is liquid phase haply carries out cooling and is then introduced into low pressure cold separator 9.Comprise hydrogen, H ₂s, NH ₃and any light hydrocarbon (it can comprise C ₁-C ₄hydrocarbon) residual gas stream 11 can purge out and send to further processing from low pressure cold separator routinely, as burning processing or fuel gas processing.In some embodiment of method of the present invention, by reclaiming hydrogen by flowing for 11 (as indicated by dotted line) with cracked gas stream 44 combinations from steam cracking device product.Bottom thing 10 from light pressure separator 9 is passed to water vapour pyrolysis zone 30.

Pollutent (that is, metal, sulphur and the nitrogen) content that the effluent 10 of hydrogenation processing comprises reduction, the paraffinicity of increase, the BMCI of reduction and American Petroleum Institute (API) (API) proportion increasing.

The effluent 10 of hydrogenation processing for example, in the situation that exist the water vapour of significant quantity (allow and enter via steam entry (not shown)) to be passed to convection zone 32.In convection zone 32, mixture is heated to preset temperature, for example, uses one or more waste heat flux or other applicable heating arrangement.The mixture through heating of light ends and water vapour is passed to steam-liquid separation section 36, usings discharge section 38 as the oil fuel component being suitable for pyrolysis fuel oil 71 blend.Remaining hydrocarbon part for example, is transported to pyrolysis section 34 to produce the product stream 39 mixing together with the light ends 22 from the first disengaging zone 20 (naphtha fraction).

Water vapour pyrolysis zone 30 operates being effective under the parameter that makes effluent 10 be cracked into required product (butylene and the pyrolysis gasoline that comprise ethene, propylene, divinyl, mixing).In certain embodiments, use following condition to carry out steam cracking: the temperature in 400 ℃ to 900 ℃ scopes in convection zone and in pyrolysis section; The water vapour of 0.3:1 to 2:1 scope and hydrocarbon ratio in convection zone; And the residence time in 0.05 second to 2 seconds scope in convection zone and in pyrolysis section.

In certain embodiments, steam-liquid separation section 36 comprises one or more vapor liquid tripping devices 80 as shown in Fig. 2 A to 2C.Vapor liquid tripping device 80 be operation economical and Maintenance free because it does not need electric power or chemistry supply.In general, device 80 comprises three ports, comprises ingress port for receiving vapour-liquid mixture, is respectively used to discharge and collect separated steam and vapor outlet port port and the liquid exit port of liquid.Device 80 line operates that are combined into based on following phenomenon, the linear velocity that comprises the mixture entering by the overall situation flow pre-rotation section change into speed of rotation, for making the controlled centrifugation of steam and liquid (resistates) pre-separation and for promoting the separated cyclonic action of steam and liquid (resistates).In order to obtain these effects, device 80 comprises pre-rotation section 88, controlled eddy flow vertical section 90 and liquid header/settling section 92.

As shown in Figure 2 B, pre-rotation section 88 is included in controlled pre-rotation element between cross section (S1) and cross section (S2) and is connected with controlled eddy flow vertical section 90 and is positioned at the connect elements between cross section (S2) and cross section (S3).From the vapor liquid mixture of entrance 82 with diameter (D1), in cross section, (S1) locates tangential access arrangement.According to following equation, the area that enters the approach section (S1) of stream be entrance 82 area at least 10%:

$\frac{\mathrm{\π}*{\left(\right[D1)]}^2}{4}---\left(1\right)$

Pre-rotation element 88 defines curve flowing-path and it is characterized by cross section constant, that reduce to outlet S2 from entrance section S1 or that increase.The outlet (S2) of controlled pre-rotation element and the ratio between entrance section (S1) are in certain embodiments in the scope of 0.7≤S2/S1≤1.4.

The speed of rotation of mixture depends on the radius-of-curvature (R1) of the medullary ray of pre-rotation element 38, and wherein said medullary ray is defined as linking the curve lines of all central points of the continuous cross-sections surfaces of pre-rotation element 88.In certain embodiments, radius-of-curvature (R1) is in the scope of 2≤R1/D1≤6, and wherein angular aperture is in the scope of 150 °≤α R1≤250 °.

Although be depicted as foursquarely generally, the cross-sectional shape at entrance S1 place can be the combination of rectangle, round rectangle, circle, ellipse or other linear, curved shape or above-mentioned shape.The shape (for example) in the cross section of the curved path of the pre-rotation element 38 passing through along fluid in certain embodiments, on the whole square shape is changed to rectangular shape progressively.The cross section of element 88 is varied to rectangular shape progressively advantageously makes port area maximize, thus allow gas in early days the stage separated with liquid mixture and obtain uniform velocity distribution, and the shear-stress of fluid in flowing minimized.

From the fluid stream of controlled pre-rotation element 88, from cross section, (S2) arrives controlled eddy flow vertical section 90 through section (S3) by described connect elements.Described connect elements be included as open and be connected to the entrance in controlled eddy flow vertical section 90 or become the open area of integral body with it.Fluid stream enters controlled eddy flow vertical section 90 to produce cyclonic action under high rotation speed.Ratio between connect elements outlet (S3) and entrance section (S2) is in certain embodiments in the scope of 2≤S3/S1≤5.

Mixture enters eddy flow vertical section 90 under high rotation speed.Kinetic energy reduce and steam under cyclonic action with liquid separation.Eddy flow forms in the upper level 90a of eddy flow vertical section 90 and lower horizontal 90b.In upper level 90a, mixture be take high vapor concentration as feature, and in lower horizontal 90b, mixture be take high strength of fluid as feature.

In certain embodiments, the inside diameter D 2 of eddy flow vertical section 90 is in the scope of 2≤D2/D1≤5 and highly can be constant along it, the length (LU) of top part 90a is in the scope of 1.2≤LU/D2≤3, and the length (LL) of bottom part 90b is in the scope of 2≤LL/D2≤5.

The end that approaches vapor outlet port 84 of eddy flow vertical section 90 is connected to the release riser tube partially opening and the pyrolysis section that is connected to water vapour pyrolysis unit.The diameter (DV) of the release riser tube partially opening is in certain embodiments in the scope of 0.05≤DV/D2≤0.4.

Therefore, in certain embodiments, and depend on the characteristic of the mixture entering, the releasing tube partially opening of the steam of large volume fraction wherein by having diameter DV is from exporting 84 separating devices 80.The liquid phase (for example, resistates) that has low vapor concentration or do not have a vapor concentration is left by the base section with cross section S4 of eddy flow vertical section 90, and is collected in liquid header and sedimentation pipe 92.

Connecting zone between eddy flow vertical section 90 and liquid header and sedimentation pipe 92 has the angle of 90 ° in certain embodiments.In certain embodiments, the internal diameter of liquid header and sedimentation pipe 92 is in the scope of 2≤D3/D1≤4 and be constant across duct length, and the length (LH) of liquid header and sedimentation pipe 92 is in the scope of 1.2≤LH/D3≤5.The liquid with low vapor volume mark is removed by having diameter DL and being positioned at the bottom of described sedimentation pipe or approaching pipeline 86 slave units of locating its bottom, and described diameter DL is in certain embodiments in the scope of 0.05≤DL/D3≤0.4.

Although various members are described dividually and have an independent part, but those of ordinary skill in the art should understand, equipment 80 can form an one-piece construction, for example, it can be casting or molded, or it can assemble from independent part, for example, by welding or in other mode, independent parts being attached together, described part may or may be inaccurately corresponding to member described herein and part.

Although should understand various size, be used as diameter and list, these values in described component parts for can be also equivalent diameter in columniform embodiment.

The product stream 39 mixing is passed to the entrance of quench zone 40, wherein quenching solution 42 (for example, water and/or pyrolysis fuel oil) via independent entrance, introduce, for example, to produce the middle mix products stream 44 through quenching of the temperature (approximately 300 ℃) with reduction, and useless quenching solution 46 is discharged from.From the gaseous mixture effluent 39 of the cracker mixture of hydrogen, methane, hydrocarbon, carbonic acid gas and hydrogen sulfide normally.Water or oil quenching cooling after, in mixture 44 multi-stage compressor district 51, (in common 4 to 6 grades) compress to produce the gaseous mixture 52 of compression.The gaseous mixture 52 of compression processes to produce the gaseous mixture 54 that exhausts hydrogen sulfide and carbonic acid gas in caustic alkali processing unit 53.Further compression in gaseous mixture 54 compressor district 55, and resulting cracked gas 56 conventionally in unit 57, stands subzero treatment so that dehydration, and by using molecular sieve to be further dried.

Cold cracked gas stream 58 from unit 57 is passed to demethanizing tower 59, from this tower, produces and contains from the hydrogen of described cracked gas stream and the overhead stream 60 of methane.From the bottoms 65 of demethanizing tower 59, be then conveyed in product separation district 70 and further process, described product separation district comprises a plurality of separation columns, comprises deethanizing column, depropanizing tower and debutanizing tower.Can also adopt the Process configuration of demethanizing tower, deethanizing column, depropanizing tower and the debutanizing tower with different order.

According to method herein, in demethanizing tower 59 places and methane separation with after hydrogen reclaims in unit 61, obtain the hydrogen 62 of the purity with common 80 volume %-95 volume %.Recovery method in unit 61 comprises that low temperature reclaims (for example,, at the temperature of approximately-157 ℃).Then hydrogen stream 62 is passed to hydrogen purification unit 64, as pressure-variable adsorption (PSA) unit, to obtain the hydrogen stream 2 with 99.9%+ purity; Or film separation unit, to obtain the hydrogen stream 2 with approximately 95% purity.The hydrogen stream 2 of purifying and then loop back with the major portion as the essential hydrogen of hydrogenation processing district.In addition, small proportion can be for the hydrogenation (not shown) of acetylene, propine and propadiene.In addition,, according to method herein, methane stream 63 can optionally be recycled in steam cracking device to be used as the fuel of burner and/or well heater.

Bottoms 65 from demethanizing tower 59 is transported to the entrance in product separation district 70 to be separated into respectively via the butylene and the pyrolysis gasoline that export 78,77,76,75,74 and 73 methane of discharging, ethene, propylene, divinyl, mixing.Pyrolysis gasoline comprises C5-C9 hydrocarbon conventionally, and can extract benzene, toluene and dimethylbenzene from this section of cut.Optionally, from the discharge section 38 of steam-liquid separation section 36 and pyrolysis fuel oil 71 (for example, the material seething with excitement at the temperature of the boiling point higher than minimum boiling point C10 compound, be called as " C10+ " stream) combination, and mixed flow for example can be drawn out of, as pyrolysis fuel oil blend 72 (, low sulphur fuel oil blend) to further process in non-at-scene refinery.

The advantage of the system of describing with respect to Fig. 1 herein comprises the hydrogen dividing potential drop that increases in reactor and via the hydrogen transference efficiency of saturated raising.In general:

PT＝PA+PB+PC。(2)

In situation of the present invention:

PT=P petroleum naphtha+PH2+PX+PY.(3)

If remove P petroleum naphtha, PT keeps identical, and therefore PH2 (and PX and PY) all increases.

Speed (saturated)=k saturated [reactant] x[pH2].(4)

System described herein also reduces solution loss, and reduces H2 consumption.This likely operates this system as the system of sealing or approximate sealing.

In certain embodiments, selective hydrogenation processing or hydroprocessing process can by aromatics (especially polyvinyl aromatic compound) saturated, follow gentle hydrocracking and increase the paraffinicity of raw material (or reducing BMCI).When hydrotreatment crude oil, pollutent as metal, sulphur and nitrogen can be by raw material be removed by the layered catalyst of the catalysis of a series of execution de-metallizations, desulfurization and/or denitrogenation.

In one embodiment, for carrying out the order of the catalyzer of hydrodemetallation (HDM) (HDM) and hydrogenating desulfurization (HDS), be as follows:

A. hydrodemetallation (HDM) catalyzer.Catalyzer in HDM section is generally based on gamma-alumina carrier, has about 140-240m ²the surface-area of/g.This catalyzer is best described as has very high volume of voids, for example, surpasses 1cm ³/ g.Pore size itself is mainly macropore conventionally.Require this point so that the large capacity of the metal picked-up on catalyst surface and optional doping agent to be provided.Conventionally the active metal on catalyst surface is the proportionally nickel of Ni/Ni+Mo<0.15 and the sulfide of molybdenum.The concentration of nickel is lower than other catalyzer on HDM catalyzer, because some nickel and vanadium expection deposit from raw material itself in removal process, thereby serves as catalyzer.The doping agent using can for one or more phosphorus (referring to, for example, U.S. Patent Publication US 2005/0211603, it is incorporated to herein by reference), boron, silicon and halogen.Catalyzer can be the form that is alumina extrudate or alumina beads.In certain embodiments, alumina beads is for promoting the unloading of the catalyzer HDM bed of reactor during by scope 30% to 100% at the place, top of bed in metal picked-up.

B. in the middle of, catalyzer also can be for carrying out the transition between HDM and HDS function.It has intermediate metal load and pore size distribution.Catalyzer in HDM/HDS reactor is essentially the carrier based on aluminum oxide that is extrudate form, from at least one catalytic metal of VI family (for example optionally exist, molybdenum and/or tungsten), and/or for example, from least one catalytic metal (, nickel and/or cobalt) of group VIII.Described catalyzer also optionally comprises the doping agent that at least one is selected from boron, phosphorus, halogen and silicon.Physical property comprises about 140-200m ²the surface-area of/g, at least 0.6cm ³the volume of voids of/g and be mesopore and the hole in 12 to 50nm scopes.

Catalyzer in c.HDS section can comprise those of the solid support material that has based on gamma-alumina, has the typical surface area towards the higher-end of HDM scope, for example about 180-240m ²the scope of/g.This required higher surface of HDS produces relatively little volume of voids, for example, and lower than 1cm ³/ g.Described catalyzer comprises at least one element from VI family (as molybdenum) and at least one element from group VIII (as nickel).Described catalyzer also comprises at least one doping agent that is selected from boron, phosphorus, silicon and halogen.In certain embodiments, cobalt is used for providing relatively high-caliber desulfurization.The metal load of active phase is higher, because required activity is higher, make like this mol ratio of Ni/Ni+Mo in 0.1 to 0.3 scope, and (Co+Ni)/Mo mol ratio is in 0.25 to 0.85 scope.

D. final catalyzer (it optionally substitutes the second and the 3rd catalyzer) is designed to carry out the hydrogenation (rather than major function of hydrogenating desulfurization) of raw material, for example, as Appl.Catal.A General, described in 204 (2000) 251.Described catalyzer also will promote and carrier will be macropore gamma-alumina by Ni.Physical property comprises the surface-area towards the higher-end of HDM scope, for example 180-240m ²/ g gr.This required higher surface of HDS produces relatively little volume of voids, for example, and lower than 1cm ³/ g.

Method and system herein provides the improvement that is better than known water vapour pyrolysis cleavage method, comprise use crude oil as raw material to produce petroleum chemicals as the ability of alkene and aromatics.Impurity is also significantly removed from initial charge as metal, sulphur and nitrogen compound in addition, and this has been avoided the aftertreatment of final product.

In addition, the hydrogen producing from steam cracking district is recycled to hydrogenation processing district, to minimize the demand to fresh hydrogen.In certain embodiments, the system of integration described herein only needs fresh hydrogen to carry out start-up operation.Once reaction reaches balance, hydrogen purification system can provide enough high-purity hydrogens, to maintain the operation of whole system.

In above and appended accompanying drawing, method and system of the present invention has been described; Yet revising will be clearly for the person of ordinary skill of the art, and protection scope of the present invention will be limited by following claims.

Claims (7)

1. for directly processing crude oil is to produce hydrotreatment and the water vapour method for pyrolysis of the integration of olefinic and aromatic base crude oil chemical products, described method comprises:

A. described crude separation is become to light component and heavy component;

B. described heavy component and hydrogen charging are extremely being effective in to the hydrogenation processing district operating under the condition of the effluent that produces hydrogenation processing, the effluent of described hydrogenation processing has the pollutant load of reduction, the U.S. mineral bureau correlation index of the paraffinicity of increase, reduction and American Petroleum Institute's proportion of increase;

C. effluent and the water vapour of described hydrogenation processing are feeded to the convection zone of water vapour pyrolysis zone;

D. heat the described mixture from step (c), and it is passed to steam-liquid separation section;

E. from described water vapour pyrolysis zone, remove the nubbin from described steam-liquid separation section;

F. will be from the light component of step (a), from the lightweight part of described steam-liquid separation section and water vapour charging to the pyrolysis section of described water vapour pyrolysis zone for thermo-cracking;

G. from described water vapour pyrolysis zone, reclaim the product stream mixing;

H. the product stream of the mixing of separated described thermo-cracking;

I. the hydrogen that purifying reclaims in step (h), and it is recycled to step (b);

J. from the mix products of described separation, flow back to receipts alkene and aromatics; And

K. from the mix products of described separation, flow back to receipts pyrolysis fuel oil.

2. integration method as claimed in claim 1, wherein

Step (h) comprises

With a plurality of compression stages, compress the mix products stream of described thermo-cracking;

The thermo-cracking mix products of described compression is flowed through be subject to caustic alkali to process to produce the mix products with the hydrogen sulfide of reduction and the thermo-cracking of carbon dioxide content to flow;

The mix products stream described in compression with the hydrogen sulfide of reduction and the thermo-cracking of carbon dioxide content;

Make the mix products stream dehydration of the hydrogen sulfide with reduction of described compression and the thermo-cracking of carbon dioxide content;

From the hydrogen sulfide with reduction of compression of described dehydration and the mix products of the thermo-cracking of carbon dioxide content, flow back to receipts hydrogen; And

From the remainder of the hydrogen sulfide with reduction of compression of described dehydration and the mix products of the thermo-cracking of carbon dioxide content stream, obtain as the alkene step (j) and aromatics and as the pyrolysis fuel oil in step (k);

And

Step (i) comprises that hydrogen that purifying flows back to receipts from the mix products of the hydrogen sulfide with reduction of the compression of described dehydration and the thermo-cracking of carbon dioxide content is for being recycled to described hydrogenation processing district.

3. integration method as claimed in claim 2, wherein flows back to and receives hydrogen and further comprise and reclaim individually methane for use as the burner described thermo-cracking step and/or the fuel of well heater from the hydrogen sulfide with reduction of compression of described dehydration and the mix products of the thermo-cracking of carbon dioxide content.

4. integration method as claimed in claim 1, wherein carries out blend by the pyrolysis fuel oil reclaiming in the described nubbin from described steam-liquid separation section and step (k).

5. integration method as claimed in claim 1, is wherein separated into vapor fraction by the effluent of the hydrogenation processing of described heating and liquid distillate is the steam-liquid separating appts using based on physics and mechanical separation.

6. integration method as claimed in claim 5, wherein said steam-liquid separating appts comprises

The pre-rotation element with entering part and transition portion, described entering part has for receiving entrance and the curved shape conduit of described mobile fluid mixture,

Controlled eddy flow section, described eddy flow section has

By the junction of described curved shape conduit and described eddy flow section, adjoin to the entrance of described pre-rotation element,

At the lifting pipeline section of the upper end of described eddy flow member, steam is by described lifting pipeline section;

And

Liquid header/settling section, liquid is by described liquid header/settling section.

7. integration method as claimed in claim 1, it further comprises:

Separated described hydrogenation processing district reactor effluent in high-pressure separator is to reclaim cleaned and be recycled to described hydrogenation processing district as the gas part in other hydrogen source; And liquid portion, and

Described liquid portion from described high-pressure separator is separated into gas part and liquid portion in light pressure separator, wherein the described liquid portion from described light pressure separator is the effluent that stands the described hydrogenation processing of thermo-cracking, and partly before the separation after described water vapour pyrolysis zone and in step (h), combines with the described product stream mixing from the described gas of described light pressure separator.