CN104093821B - For the directly hydrotreating for including the integration that hydrogen is redistributed of processing crude oil and steam pyrolysis method - Google Patents
For the directly hydrotreating for including the integration that hydrogen is redistributed of processing crude oil and steam pyrolysis method Download PDFInfo
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- CN104093821B CN104093821B CN201380006605.5A CN201380006605A CN104093821B CN 104093821 B CN104093821 B CN 104093821B CN 201380006605 A CN201380006605 A CN 201380006605A CN 104093821 B CN104093821 B CN 104093821B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of thermal cracking in the absence of hydrogen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
- C10G9/36—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
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- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention provide it is a kind of be directed to be integrated including the hydrogenation processing district that hydrogen is redistributed steam pyrolysis area, to allow directly to process crude oil material so as to the method for producing the petroleum chemicals including alkene and aromatic compound.For directly processing crude oil so that the hydrotreating and steam pyrolysis method that produce the integration of olefinic and aromatic base crude oil chemical products include：The crude oil is separated into light components and heavy component；The heavy component and hydrogen are fed to the hydrogenation processing district operated under conditions of the effluent of processing is being hydrogenated with effective in producing, the effluent of the hydrogenation processing has pollutant load, increased paraffinicity, the Bureau of Mines Correlation index and increased American Petroleum Institute's proportion of reduction of reduction；The effluent and vapor of the hydrogenation processing are fed to the convection section in steam pyrolysis area；D. the mixture of the convection section from steam pyrolysis area is heated, and it is transferred to vapor liquid segregation section；The nubbin from the vapor liquid segregation section is removed from the steam pyrolysis area；By the light components from the initial process step, light fraction and vapor from the vapor liquid segregation section feed to the pyrolysis section in the steam pyrolysis area；The product stream of mixing is reclaimed from the steam pyrolysis area；Separate the product stream of the mixing；The hydrogen reclaimed from the product stream of the mixing is purified, and it is recycled to the hydrogenation processing district；And flow back to receipts alkene and aromatic compound from the mix products of the separation.
Description
Related application
The rights and interests for the U.S. Provisional Patent Application No. 61/591,814 submitted this application claims on January 27th, 2012, it is described
The disclosure of application is incorporated herein in its entirety by reference.
Background of invention
Invention field
It is used to directly process crude oil the present invention relates to one kind to produce petroleum chemicals such as alkene and aromatic compound
Integration hydrotreating and steam pyrolysis method.
Description of Related Art
Light alkene (that is, ethene, propylene, butylene and butadiene) and aromatic compound (that is, benzene, toluene and two
Toluene) it is widely used basic intermediate in petrochemistry and chemical industry.Thermal cracking or steam pyrolysis are generally to deposit
It is used for the major type of method for forming these materials in the case of vapor and in the case of in the absence of oxygen.For water
The raw material of steam pyrolysis can include oil gas and distillate such as naphtha, kerosene and gas oil.These raw materials are obtained
Property is typically limited and needs expensive and energy-intensive the method and step in crude oil refineries.
The raw material using heavy hydrocarbon as steam pyrolysis reactor is studied.Conventional heavy hydrocarbon pyrolysis operations
In major defect be coke formation.For example, the steam pyrolysis method for heavy liquid hydrocarbon is disclosed in U.S. Patent number 4,
In 217,204, wherein the spray of fused salt is incorporated into steam pyrolysis reaction zone to attempt to minimize coke formation.Make
In an example with the Arabian light crude of the Conradson carbon residue with 3.1 weight %, cracking apparatus can be present
Ongoing operation 624 hours in the case of fused salt.In the comparison example without fused salt, steam pyrolysis reactor is small only 5
When after become clogged up and inoperable due to the formation of coke in reactor.
In addition, using heavy hydrocarbon as the alkene of the raw material of steam pyrolysis reactor and aromatic compound yield and
Be distributed different from the use of hydrocarbon feedstock those.Heavy hydrocarbon have the aromatic content higher than light hydrocarbon, such as by compared with
Indicated by high Bureau of Mines Correlation index (BMCI).BMCI is the measurement of the armaticity of raw material and is calculated as follows：
BMCI=87552/VAPB+473.5* (sp.gr.) -456.8 (1)
Wherein：
Volume average boiling points of the VAPB=in terms of rankine degree (degrees Rankine), and
The proportion of sp.gr.=raw materials.
As BMCI is reduced, ethylene yield is expected increase.Therefore, for steam pyrolysis, highly paraffinic or low virtue
Fragrant compounds of group charging is typically preferred, so as to obtain the required alkene of higher yields and avoid higher unwanted production
Coke formation in thing and reactor coil section.
Absolute coke formation speed in steam pyrolysis device is by Cai et al., " Coke Formation in Steam
Crackers for Ethylene Production, " Chem.Eng.＆Proc., volume 41, (2002), 199-214 is carried out
Report.In general, absolute coke formation speed is according to alkene>Aromatic compound>The incremental order of alkane, wherein alkene
Hydrocarbon represents heavy olefins.
, can be with other classes of relatively large acquisition in order to the demand in response to the growth to these petroleum chemicals
The charging of type such as crude oil are attractive for the producer.Refinery will be minimized or eliminated using crude oil feeding at these
Occurs the possibility of bottleneck in the production of petroleum chemicals.
Although steam pyrolysis method well develops and is suitable for its predetermined purpose, the selection of raw material has very much always
Limit.
Summary of the invention
This paper system and method provide a kind of steam pyrolysis area integrated with the hydrogenation processing district including hydrogen redistribution
Petroleum chemicals, including alkene and aromatic compound are produced to allow directly to process crude oil material.
Steamed for directly processing crude oil with the hydrotreating and water that produce the integration of olefinic and aromatic base crude oil chemical products
Gas method for pyrolysis includes：The crude oil is separated into light components and heavy component；By the heavy component and hydrogen feed to
The hydrogenation processing district operated under conditions of effluent effective in producing hydrogenation processing, the effluent of the hydrogenation processing has drop
Low pollutant load, increased paraffinicity, the Bureau of Mines Correlation index of reduction and increased american petroleum
Can proportion；The effluent and vapor of the hydrogenation processing are fed to the convection section in steam pyrolysis area；D. heating comes from water
The mixture of the convection section of steam pyrolysis zone, and it is transferred to vapor-liquid segregation section；From the vapor
Pyrolysis zone removes the nubbin from the vapor-liquid segregation section；By the light components from the initial process step,
Light fraction and vapor from the vapor-liquid segregation section feed to the pyrolysis section in the steam pyrolysis area；From
Reclaim the product stream of mixing in the steam pyrolysis area；Separate the product stream of the mixing；Purify the product stream from the mixing
The hydrogen of recovery, and it is recycled to the hydrogenation processing district；And from the mix products of the separation flow back to receipts alkene and
Aromatic compound.
As used herein, term " crude oil " should be read to include the whole crude from usual sources, have been subjected to
The crude oil of pretreatment.Term crude oil, which will also be understood to include, is already subjected to water-oil separation and/or gas-oil separation and/or desalination
And/or stabilized crude oil.
Other side, embodiment and the advantage of the method for the present invention are discussed further below.Further, it should be understood that foregoing
Information and it is described below be all only the illustrative example of various aspects and embodiment, and aim to provide required for understanding
The general survey or framework of the feature of protection and the property of embodiment and characteristic.Accompanying drawing is illustrative and is provided to further
Understand the different aspect and embodiment of the method for the present invention.
Brief description
The present invention will following and be explained in further detail referring to the drawings, wherein：
Fig. 1 is the method flow diagram of the embodiment of integration method described herein；And
Fig. 2A to Fig. 2 C is some embodiments according to the steam pyrolysis unit in integration method described herein
Used in the exemplary illustration that carries out of the perspective view of vapor-liquid separator, top view and side view.
Detailed description of the invention
Figure 1 illustrates the hydrogenation processing of the integration including being redistributed with hydrogen and the side of steam pyrolysis method and system
Method flow chart.The system of the integration generally comprises initial charge Disengagement zone 20, selective catalytic hydrogenation processing district, vapor
Pyrolysis zone 30 and product Disengagement zone.
In general, crude oil feeding is flashed, (boiling point is further being cracked containing minimum requirement lighter fraction whereby
Hydrocarbon and containing being easy in the range of the hydrogen of release, for example, be up to about 185 DEG C) steam pyrolysis area is shown delivered directly to, and only must
The cut wanted, i.e., carry out hydrogenation processing with the cut less than predetermined hydrogen content.This is favourable, because it is processed in hydrogenation
Increased hydrogen dividing potential drop is provided in reactor, so as to improve the efficiency of hydrogen migration via saturation.This will the loss of reduction hydrogen solution and H2
Consumption.The hydrogen for being easy to release contained in crude oil feeding is redistributed to maximize the yield of the product such as ethene.Hydrogen is again
Distribution allows the increased generation of the overall reduction and light olefin of heavy product.
First Disengagement zone 20 includes the entrance for being used to receive raw material stream 1, the outlet for discharging light fraction 22, Yi Jiyong
In the outlet of discharge heavy end 226.Disengagement zone 20 can be single-stage separator, and such as cut point is in about 150 DEG C to about 260 DEG C models
Enclose interior flash separator.In certain embodiments, light fraction 22 can be naphtha cut.Table 1 is shown based on different points
Evaporate hydrogen content a little.
In a further embodiment, Disengagement zone 20 includes eddy flow phase-separating device or the physics based on steam and liquid
Or mechanically decoupled other separators or consisting essentially of (that is, being operated in the case of in the absence of flash zone).Steam-
One example of liquid separating appts by and reference picture 2A to Fig. 2 C illustrate.Vapor-liquid separator it is similar
Arrangement is also described in U.S. Patent Publication number 2011/0247500, and the patent is incorporated herein in its entirety by reference.
The Disengagement zone includes the separator being physically or mechanically separated or consisting essentially of implementation based on steam and liquid
In scheme, cut point can be adjusted based on the fluid velocity of gasification temperature and the material for entering device
Table 1
| The boiling point (DEG C) of light fraction | Hydrogen content (%) |
| 150 | 15.22 |
| 180 | 14.88 |
| 200 | 14.73 |
| 260 | 14.34 |
Being hydrogenated with processing district includes the hydrogenation processing reaction zone 4 with entrance, and the entrance is used to receive light fractions 21
With the mixture of hydrogen 2 recycled from steam pyrolysis product stream and supplementing hydrogen when necessary.Hydrogenation processing reaction zone 4 is further
Include the outlet of the effluent 5 for discharging hydrogenation processing.
Reactor effluent 5 from one or more of hydrogenation processing reactors enters in heat exchanger (not shown)
Row cools down and delivers to high-pressure separator 6.Separator headpiece 7 is cleaned in amine unit 12 and resulting is rich in hydrogen
Gas stream 13 be passed to recycle compressor 14 so as to it is described hydrogenation processing reactor in be used as recycle gas 15.Come
Cooled down from the bottoms 8 in generally liquid form of high-pressure separator 6 and be introduced to low pressure cold separator 9,
Bottoms are separated into gas stream and liquid flow 10 described in the low pressure cold separator.Gas from low pressure cold separator
Including hydrogen, H2S、NH3And any light hydrocarbon such as C1-C4Hydrocarbon.These usual gases are conveyed to be processed further such as burning processing
(flare processing) or fuel gas are processed.According to this paper some embodiments, by the way that hydrogen, H will be included2S、NH3With
And any light hydrocarbon such as C1-C4The water vapor gas stream 11 of hydrocarbon is combined to reclaim hydrogen with steam pyrolysis device product 44.Liquid
All or part of charging as steam pyrolysis area 30 of stream 10.
Steam pyrolysis area 30 generally comprises convection section 32 and pyrolysis section 34, and the pyrolysis section can be based on this area
The steam pyrolysis unit known operates to be operated, i.e., by thermal cracking feed charge to described in the case where there is vapor
Convection section.In addition, being steamed in some optional embodiments as described herein (as indicated by using dotted line in Fig. 1)
Solution-air body segregation section 36 is included between section 32 and section 34.What the steam pyrolysis charging of the heating from convection section 32 passed through
Vapor-liquid segregation section 36 can be the separator being physically or mechanically separated based on steam and liquid.
In one embodiment, vapor-liquid separator by and reference picture 2A to Fig. 2 C illustrate.Steam
The similar arrangement of solution-air body separator is also described in U.S. Patent Publication number 2011/0247500, and the patent is to quote
Mode be integrally incorporated herein.In this device, steam and liquid are flowed through with eddy flow geometry, thus described device
Isothermally and under the low-down residence time operate.In general, steam is vortexed to produce power with circular pattern, heavier
Drop and liquid are treated captured and are directed across to liquid outlet as fuel oil 38, for example, it is added into pyrolysing fuel
Oily blend, and steam is guided through vapor outlet port as the charging 37 of pyrolysis section 34.Gasification temperature and fluid velocity quilt
Change to adjust approximate temperature separation, such as it is compatible with residual fuel oil blend in certain embodiments, such as about
540℃。
Quenching area 40 is included with the entrance of the outlet in fluid communication in steam pyrolysis area 30, for allowing quenching solution
42 entrances entered, the outlet of the product stream 44 of the mixing quenched for discharge and the outlet for discharging quenching solution 46.
In general, the product stream 44 of the middle mixing by quenching is converted to intermediate product stream 65 and hydrogen 62, and hydrogen exists
Purified in the inventive method and be used as recycle hydrogen air-flow 2 in hydrogenation processing reaction zone 4.Intermediate product stream 65 is usual
Final product and residue are fractionated into Disengagement zone 70, the Disengagement zone can be one or more separative elements, such as multiple
Fractionating column, including dethanizer, depropanizing tower and debutanizing tower, for example as one of ordinary skill in the art known in.
For example, suitable equipment is described in " Ethylene, " Ullmann ' s Encyclopedia of Industrial
Chemistry, volume 12, page 531 to page 581, specifically in Figure 24, Figure 25 and Figure 26, the document is to quote
Mode is incorporated herein
In general, product Disengagement zone 70 includes being in what is be in fluid communication with product stream 65 and multiple product exits 73 to 78
Entrance, the multiple product exit is included for the outlet 78 for discharging methane, the outlet 77 for discharging ethene, for discharging third
The outlet 76 of alkene, the outlet 75 for discharging butadiene, for discharge mixing butylene outlet 74 and for discharge pyrolysis
The outlet 73 of gasoline.Further it is provided that the outlet for discharging pyrolysis fuel oil 71.Optionally, from vapor-liquid segregation section 36
Fuel oil part 38 and pyrolysis fuel oil 71 it is combined and can be extracted as pyrolysis fuel oil blend 72, for example, having
Stay in the low sulphur fuel oil blend being processed further in non-at-scene refinery.It should be noted that though it is shown that six products
Outlet, can depend on the arrangement of separative element that (for example) is used and yield and Spreading requirements and provide less or more
Products export.
In the embodiment using the method for the arrangement shown in Fig. 1, crude oil material 1 is separated into the first Disengagement zone 20
Light fraction 22 and heavy end 21.Light fraction 22 is transported to the hot stage 36, that is, bypass hydrogenation processing district, with vapor
The intermediate product moiety of cracking is combined and produces mix products stream as described herein.
Heavy end 21 is mixed with the hydrogen 2 and 15 of effective dose combines stream 3 to be formed.By mixture 3 at 300 DEG C extremely
Fed at temperature in 450 DEG C of scopes to selective hydrogenation and process the entrance of reaction zone 4.In certain embodiments, hydrogenation adds
Work reaction zone 4 includes such as jointly owned U.S. Patent Publication number 2011/0083996 and PCT Patent Application publication No. WO2010/
009077th, one or more units behaviour described in WO2010/009082, WO2010/009089 and WO2009/073436
Make, the patent is all incorporated herein in its entirety by reference.For example, hydrogenation processing district can include adding containing effective dose
One or more beds of hydrogen catalyst for demetalation, and there is Hydrodearomatization, hydrodenitrogeneration, hydrodesulfurization containing effective dose
And/or one or more beds of the hydrogenation processing catalyst of hydrocracking function.In a further embodiment, hydrogenation processing is anti-
Area 4 is answered to include more than two catalyst bed.In other embodiments, hydrogenation processing reaction zone 4 include each containing one or
Multiple reaction vessels of the catalyst bed of multiple (such as) difference in functionalitys.
Hydrogenation processing reaction zone 4 effective in make crude oil material HDM, Hydrodearomatization, hydrodenitrogeneration, plus
Operated under the parameter of hydrogen desulfurization and/or hydrocracking.In certain embodiments, hydrogenation processing is carried out using following condition：
Operation temperature in 300 DEG C to 450 DEG C scopes；In operating pressure of 30 bars into 180 bar scopes；And in 0.1h-1To 10h-1
Liquid hourly space velocity (LHSV) in scope.
Reactor effluent 5 from hydrogenation processing district 4 is cooled down in exchanger (not shown) and delivers to high pressure
Cold or heat separator 6.Separator headpiece 7 is cleaned and the resulting quilt of gas stream 13 rich in hydrogen in amine unit 12
Recycle compressor 14 is transferred to be used as recycling gas 15 in hydrogenation processing reaction zone 4.In coming for generally liquid phase
Cooled down from the separator bottom thing 8 of high-pressure separator 6 and be then introduced to low pressure cold separator 9.Include hydrogen, H2S、NH3
And (it can include C to any light hydrocarbon1-C4Hydrocarbon) residual gas stream 11 routinely can be purged out simultaneously from low pressure cold separator
And send to and be processed further, such as burning processing or fuel gas processing.In some embodiments of the method for the present invention, pass through
11 (as indicated by the dashed line) of stream are combined with the cracked gas stream 44 from steam pyrolysis device product to reclaim hydrogen.From low
The bottoms 10 of pressure separator 9 is passed to steam pyrolysis area 30.
Pollutant (that is, metal, the sulphur and nitrogen) content of effluent 10 comprising reduction of hydrogenation processing, increased alkane
Content, the BMCI and increased American Petroleum Institute (API) (API) proportion of reduction.
The effluent 10 of hydrogenation processing (is for example allowed in the vapor that there is effective dose via steam entry (not shown)
Enter) in the case of be passed to convection section 32.In convection section 32, mixture is heated to predetermined temperature, for example, using
One or more waste heat flux or other suitable heating arrangements.The mixture by heating of light fraction and vapor is passed
To vapor-liquid segregation section 36, the fuel oil ingredient for being suitable for being blended with pyrolysis fuel oil 71 is used as using discharge part 38.It is remaining
Hydrocarbon part be transported to pyrolysis section 34 together with the light fraction 22 (such as naphtha cut) from the first Disengagement zone 20
To produce the product stream 39 of mixing.
Steam pyrolysis area 30 effective in make effluent 10 be cracked into required product (including ethene, propylene, butadiene,
The butylene and pyrolysis gasoline of mixing) parameter under operate.In certain embodiments, vapor is carried out using following condition to split
Solution：Temperature in convection section and in pyrolysis section in 400 DEG C to 900 DEG C scopes；0.3 in convection section:1 to 2:The vapor of 1 scope
With hydrocarbon ratio；And the residence time in convection section and in pyrolysis section in 0.05 second to 2 seconds scope.
In certain embodiments, vapor-liquid segregation section 36 includes one or more steamings as shown in Fig. 2A to 2C
Gas-liquid separator 80.Vapor liquid separator 80 is operation economy and Maintenance free, because it need not electricity
Power or chemistry supply.In general, device 80 includes three ports, including for receiving the arrival end of vapour-liquid mixture
Mouthful, be respectively used to discharge and collect separated steam and the vapor outlet port port of liquid and fluid outlet port.The base of device 80
Operated in the combination of following phenomenon, including the linear velocity of the mixture of entrance changes into rotation by overall situation flowing pre-rotation section
Rotary speed, the controlled centrifugal action for making steam and liquid (residue) pre-separation and for promoting steam and liquid (residual
Excess) separation cyclonic action.In order to obtain these effects, device 80 includes 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 the controlled pre-rotation element between section (S1) and section (S2)
And the connecting element for being connected and being located between section (S2) and section (S3) with controlled eddy flow vertical section 90.From with straight
The vapor liquid mixture of the entrance 82 in footpath (D1) tangentially enters equipment at section (S1) place.According to below equation, enter what is become a mandarin
The area of approach section (S1) is at least the 10% of the area of entrance 82：
Pre-rotation element 88 defines curvilinear flow path and is characterized in that constant from entrance section S1 to outlet S2
, reduce or increased section.Ratio between the outlet (S2) of controlled pre-rotation element and entrance section (S1)
In certain embodiments in the scope of 0.7≤S2/S1≤1.4.
The rotary speed of mixture depends on the radius of curvature (R1) of the center line of pre-rotation element 38, wherein the center
Line is defined as linking the curved lines of all central points of the continuous cross-sections surfaces of pre-rotation element 88.In some embodiments
In, 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 it is generally square, cross sectional shape entrance S1 at can be rectangle, round rectangle,
The combination of circular, ellipse or other linears, shaped form or above-mentioned shape.In certain embodiments, pass through along fluid
Square shape is progressively changed to rectangle shape to the shape (such as) in the section of the curved path of pre-rotation element 38 on the whole
Shape.The section of element 88 progressively change it is in a rectangular shape advantageously maximize aperture area so that allow gas early stage
Stage separates with liquid mixture and obtains uniform VELOCITY DISTRIBUTION, and minimizes the shear stress in flow of fluid.
Fluid stream from controlled pre-rotation element 88 from section (S2) by section (S3) by the connecting element to
Up to controlled eddy flow vertical section 90.The connecting element includes for opening and is connected in controlled eddy flow vertical section 90
Entrance or the open area integral with it.Fluid stream enters controlled eddy flow vertical section 90 to produce rotation at a high rotational speed
Stream is acted on.Ratio between connecting element outlet (S3) and entrance section (S2) is in certain embodiments in 2≤S3/S1
In≤5 scope.
Mixture enters eddy flow vertical section 90 at a high rotational speed.Kinetic energy reduce and steam under cyclonic action with liquid
Body is separated.Eddy flow is formed in the upper level 90a and lower horizontal 90b of eddy flow vertical section 90.In upper level 90a, mix
Compound is characterized with high vapor concentration, and in lower horizontal 90b, mixture is characterized with high strength of fluid.
In certain embodiments, the internal diameter D2 of eddy flow vertical section 90 is in the range of 2≤D2/D1≤5 and high along it
Degree can be constant, and upper part 90a length (LU) is in the range of 1.2≤LU/D2≤3, and low portion 90b length
(LL) is spent in the range of 2≤LL/D2≤5.
The end close to vapor outlet port 84 of eddy flow vertical section 90 is connected to the release riser partially opened and connected
To the pyrolysis section of steam pyrolysis unit.The diameter (DV) of the release riser partially opened is in certain embodiments 0.05
In the scope of≤DV/D2≤0.4.
Therefore, in certain embodiments, and depending on the characteristic of the mixture entered, large volume fraction therein
Steam by the release pipe partially opened with diameter DV from outlet 84 separating devices 80.With low vapor concentration or do not deposit
Left in the liquid phase (for example, residue) of vapor concentration by the base section with cross section S4 of eddy flow vertical section 90,
And collect in liquid header and sedimentation pipe 92.
Join domain between eddy flow vertical section 90 and liquid header and sedimentation pipe 92 has in certain embodiments
90 ° of angle.In certain embodiments, the internal diameter of liquid header and sedimentation pipe 92 in the scope of 2≤D3/D1≤4 simultaneously
And for across duct length it is constant, and liquid header and sedimentation pipe 92 length (LH) 1.2≤LH/D3≤5 scope
In.Liquid with low vapor volume fraction passes through with diameter DL and positioned at the bottom of the sedimentation pipe or close to its bottom
The slave unit of pipeline 86 at place is removed, and the diameter DL is in certain embodiments in the scope of 0.05≤DL/D3≤0.4.
Although various components are dividually described and with single part, one of ordinary skill in the art
It should be understood that equipment 80 is formed as an overall structure, for example, it can be casting or molding, or it can be from independent
Part assembled, for example, by welding or being otherwise attached together single part, the part may
Or may inaccurately correspond to component described herein and part.
It should be understood that although various sizes are listed as diameter, these values are not cylindrical reality in the component parts
Applying in scheme can also be equivalent diameter.
The product stream 39 of mixing is passed to the entrance of quenching area 40, and wherein quenching solution 42 is (for example, water and/or pyrolysis
Fuel oil) introduced via single entrance, to produce the middle by the mixed of quenching of the temperature (e.g., from about 300 DEG C) with reduction
Product stream 44 is closed, and useless quenching solution 46 is discharged.Admixture of gas effluent 39 from cracker is typically hydrogen, first
Alkane, hydrocarbon, the mixture of carbon dioxide and hydrogen sulfide.After with water or oil hardening cooling, mixture 44 is in compound compressor area
It is compressed to produce the admixture of gas 52 of compression (in usual 4 to 6 grades) in 51.The admixture of gas 52 of compression is in caustic alkali
The admixture of gas 54 that hydrogen sulfide and carbon dioxide are exhausted with generation is handled in processing unit 53.Admixture of gas 54 is in pressure
Further compressed in Suo Ji areas 55, and resulting cracked gas 56 generally is subjected to low-temperature treatment to take off in unit 57
Water, and be further dried by using molecular sieve.
Cold cracked gas stream 58 from unit 57 is passed to domethanizing column 59, produces and contains from described from the tower
The hydrogen of cracked gas stream and the overhead stream 60 of methane.Then bottoms 65 from domethanizing column 59 are conveyed in product point
It is processed further from area 70, the product Disengagement zone includes multiple fractionating columns, including dethanizer, depropanizing tower and debutanization
Tower.The Process configuration of the domethanizing column with different order, dethanizer, depropanizing tower and debutanizing tower can also be used.
According to methods herein, with methane separation and after hydrogen retrieval, being had in unit 61 at domethanizing column 59
There is the hydrogen 62 of usual 80 volume %-95 volumes % purity.Recovery method in unit 61 include low temperature reclaim (for example, about-
At a temperature of 157 DEG C).Then hydrogen stream 62 is passed to hydrogen purification unit 64, such as pressure-variable adsorption (PSA) unit, to be had
There is the hydrogen stream 2 of 99.9%+ purity；Or film separation unit, to obtain the hydrogen stream 2 with about 95% purity.The hydrogen of purifying
Stream 2 and then the major part for being recycled back the required hydrogen for use as hydrogenation processing district.In addition, small scale can be used for acetylene,
The hydrogenation (not shown) of propine and allene.In addition, according to methods herein, methane stream 63 can be recycled optionally
Into steam pyrolysis device so as to the fuel as burner and/or heater.
Bottoms 65 from domethanizing column 59 are transported to the entrance of product Disengagement zone 70 to be separated into difference
Via the methane of the discharge of outlet 78,77,76,75,74 and 73, ethene, propylene, butadiene, the butylene of mixing and pyrolysis vapour
Oil.Pyrolysis gasoline generally comprises C5-C9 hydrocarbon, and can extract benzene, toluene and dimethylbenzene from this section of cut.Optionally,
Discharge part 38 from vapor-liquid segregation section 36 is with pyrolysis fuel oil 71 (for example, higher than minimum boiling point C10 compounds
Boiling point at a temperature of the material that seethes with excitement, be referred to as " C10+ " stream) combination, and mixed flow can be extracted as pyrolysis fuel oil
Blend 72 (for example, low sulphur fuel oil blend) in non-at-scene refinery to be processed further.
What the advantage herein in relation to Fig. 1 systems described was improved including increased hydrogen dividing potential drop in reactor and via saturation
Hydrogen migration efficiency.In general：
PT=PA+PB+PC. (2)
In the present case：
PT=P naphthas+PH2+PX+PY. (3)
If removing P naphthas, PT keeps identical, and therefore PH2 (and PX and PY) all increases.
Speed (saturation)=k saturations [reactant] x [pH2]. (4)
System described herein also reduces solution loss, and reduces H2 consumption.This causes this system possible as envelope
The system closed or approximately closed is operated.
In certain embodiments, selective hydrogenation processing or hydrotreating method can be (outstanding by aromatic compound
It is polyvinyl aromatic compound) saturation, then gentle hydrocracking increase paraffinicity (or the reduction of raw material
BMCI).When hydrotreating crude oil, pollutant such as metal, sulphur and nitrogen can be by making raw material pass through a series of de- gold of execution
The layered catalyst of categoryization, desulfurization and/or the catalysis of denitrogenation is removed.
In one embodiment, for carry out hydrodemetallisation (HDM) and hydrodesulfurization (HDS) catalyst it is suitable
Sequence is as follows：
A. hydrodemetallisation catalyst.Catalyst in HDM sections is generally based on gamma-alumina carrier, with about 140-
240m2/ g surface area.This catalyst is best described as with very high pore volume, for example, more than 1cm3/g.Hole
Gap size is usually predominantly macropore in itself.It is required that this point with catalyst surface is provided and optional dopant on metal take the photograph
The Large Copacity taken.Active metal on usual catalyst surface is proportionally Ni/Ni+Mo<0.15 nickel and the sulfide of molybdenum.
The concentration of nickel is lower than other catalyst on HDM catalyst, because some nickel and vanadium are it is contemplated that in removal process from raw material in itself
Deposition, so as to serve as catalyst.Used dopant can be one or more phosphorus (see, e.g., U.S. Patent Publication number
US 2005/0211603, it is hereby incorporated herein by), boron, silicon and halogen.Catalyst can be in oxidation aluminium extruded
Go out the form of thing or alumina beads.In certain embodiments, alumina beads are used in metal intake at the top of bed
By the unloading of catalyst HDM promoted in 30% to 100% scope in reactor.
B. Intermediate Catalyst can be used for carrying out the transition between HDM and HDS functions.It has intermetallic metal load and
Pore size distribution.Catalyst in HDM/HDS reactors is substantially the carrier based on aluminum oxide in extrudate form, is appointed
There is at least one catalytic metal (for example, molybdenum and/or tungsten) from group vi in selection of land, and/or from group VIII at least
A kind of catalytic metal (for example, nickel and/or cobalt).The catalyst also optionally comprising it is at least one selected from boron, phosphorus, halogen and
The dopant of silicon.Physical characteristic includes about 140-200m2/ g surface area, at least 0.6cm3/ g pore volume and for mesopore simultaneously
And in 12 holes into 50nm scopes.
Catalyst in c.HDS sections may include those with the carrier material based on gamma-alumina, with towards HDM models
The typical surface area for the higher-end enclosed, e.g., from about 180-240m2/ g scope.HDS this required higher surface produces phase
To less pore volume, for example, less than 1cm3/g.The catalyst includes at least one element (such as molybdenum) from group vi
With at least one element (such as nickel) from group VIII.The catalyst is also selected from boron, phosphorus, silicon and halogen comprising at least one
The dopant of element.In certain embodiments, cobalt is used to provide relatively high-caliber desulfurization.The Metal Supported of active phase be compared with
It is high because required activity is higher, so that Ni/Ni+Mo mol ratio in 0.1 to 0.3 scope, and (Co+Ni)/
Mo mol ratios are in 0.25 to 0.85 scope.
D. final catalyst (it optionally substitutes second and the 3rd catalyst) be designed to carry out raw material hydrogenation (and
It is not the major function of hydrodesulfurization), such as such as Appl.Catal.A General, described in 204 (2000) 251.It is described
Catalyst will also be promoted by Ni and carrier will be macropore gamma-alumina.Physical characteristic includes the higher-end towards HDM scopes
Surface area, such as 180-240m2/g gr.HDS this required higher surface produces relatively small pore volume, example
Such as, less than 1cm3/g。
Methods herein and system provide the improvement better than known steam pyrolysis cleavage method, make including the use of crude oil
For raw material to produce the ability of petroleum chemicals such as alkene and aromatic compound.Other impurity such as metal, sulphur and nitridation
Compound is also significantly removed from initial charge, and this avoids the post processing of final product.
In addition, the hydrogen produced from steam pyrolysis area 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 flat
Weighing apparatus, hydrogen purification system can provide enough high-purity hydrogens, to maintain the operation of whole system.
The method and system of the present invention is had been described for more than and in appended accompanying drawing；However, modification is for the general of this area
It will be apparent for logical technical staff, and protection scope of the present invention will be limited by claims below.
Claims (6)
1. a kind of be used to directly process crude oil to produce hydrotreating and the water of the integration of olefinic and aromatic base crude oil chemical products
Steam method for pyrolysis, methods described includes：
A. the crude oil is separated into light components and heavy component；
B. the heavy component and hydrogen are fed to the hydrogenation operated under conditions of the effluent effective in producing hydrogenation processing
Processing district, the effluent of the hydrogenation processing has the pollutant load of reduction, increased paraffinicity, U.S.'s ore deposit of reduction
Business office's correlation index and increased American Petroleum Institute's proportion；
C. the effluent and vapor of the hydrogenation processing are fed to the convection section in steam pyrolysis area；
D. mixture of the heating from step (c), and the effluent for being processed the hydrogenation of heating using vapor-liquid segregation section
Vapor fraction and liquid distillate are separated into, wherein the vapor-liquid segregation section includes：
Pre-rotation element for the linear velocity of the mixture of entrance to be changed into rotary speed, the pre-rotation element includes
Entering part, the entering part has entrance and is connected to the shaped form conduit of the entrance, the entering part across
More to connecting element,
Controlled eddy flow section, the eddy flow section has
Adjoined at the connecting element by the meeting point of the shaped form conduit and eddy flow section to pre-rotation member
The entrance of part, and
In the lifting pipeline section of the upper end of eddy flow component, steam passes through the lifting pipeline section；And
Liquid header/settling section, liquid passes through the liquid header/settling section；
E. the nubbin from the vapor-liquid segregation section is removed from the steam pyrolysis area；
F. the light components of step (a) will be come from, light fraction and vapor charging from the vapor-liquid segregation section
Pyrolysis section to the steam pyrolysis area is used for thermal cracking；
G. the product stream of mixing is reclaimed from the steam pyrolysis area；
H. the product stream of the mixing of thermal cracking is separated；
I. the hydrogen reclaimed in step (h) is purified, and it is recycled to step (b)；
J. receipts alkene and aromatic compound are flowed back to from the mix products of the separation；And
K. receipts pyrolysis fuel oil is flowed back to from the mix products of the separation.
2. the cut point in the method as described in claim 1, wherein step (a) is 150 DEG C to 260 DEG C.
3. the method as described in claim 1, wherein
Step (h) includes
The mix products stream of the thermal cracking is compressed with multiple compression stages；
Make compression thermal cracking mix products flow through by causticity alkali process with produce have reduction hydrogen sulfide and carbon dioxide contain
The mix products stream of the thermal cracking of amount；
The mix products stream of the thermal cracking of the compression hydrogen sulfide with reduction and carbon dioxide content；
Make the mix products stream dehydration of the thermal cracking with the hydrogen sulfide reduced and carbon dioxide content of the compression；
Receipts hydrogen is flowed back to from the mix products of the thermal cracking with the hydrogen sulfide reduced and carbon dioxide content of the compression of dehydration；With
And
From the compression of the dehydration have reduction hydrogen sulfide and carbon dioxide content thermal cracking mix products stream it is surplus
Remaining part is separately won such as the alkene and aromatic compound in step (j) and such as the pyrolysis fuel oil in step (k)；
And
Step (i) includes purifying from the thermal cracking with the hydrogen sulfide reduced and carbon dioxide content of the compression of the dehydration
Mix products flow back to the hydrogen of receipts to be recycled to the hydrogenation processing district.
4. method as claimed in claim 3, wherein the hydrogen sulfide and carbon dioxide with reduction of the compression from the dehydration
The mix products of the thermal cracking of content flow back to receipts hydrogen and further comprise individually reclaiming methane for use as in the cracking step
Burner and/or heater fuel.
5. the method as described in claim 1, wherein by the nubbin and step from the vapor-liquid segregation section
(k) pyrolysis fuel oil reclaimed in is blended.
6. the method as described in claim 1, it further comprises：
Hydrogenation processing district reactor effluent is separated in high-pressure separator and is cleaned to reclaim and is recycled to institute
State the gas part that hydrogenation processing district is originated as other hydrogen；And liquid portion, and
The liquid portion from the high-pressure separator is separated into gas part and liquid portion in low pressure separator,
The wherein liquid portion from the low pressure separator is the effluent for the hydrogenation processing for being subjected to thermal cracking, and comes
From before separation of the gas part of the low pressure separator after the steam pyrolysis area and in step (h)
It is combined with the product stream mixed.
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| CN201710589272.3A CN107216914B (en) | 2012-01-27 | 2013-01-27 | Integrated hydrotreating and steam pyrolysis process including hydrogen redistribution for direct processing of crude oil |
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| US201261591814P | 2012-01-27 | 2012-01-27 | |
| US61/591,814 | 2012-01-27 | ||
| PCT/US2013/023336 WO2013112969A2 (en) | 2012-01-27 | 2013-01-27 | Integrated hydrotreating and steam pyrolysis process including hydrogen redistribution for direct processing of a crude oil |
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| JP (2) | JP6151717B2 (en) |
| KR (1) | KR102071654B1 (en) |
| CN (2) | CN104093821B (en) |
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| WO (1) | WO2013112969A2 (en) |
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| JP6242379B2 (en) * | 2012-03-20 | 2017-12-06 | サウジ アラビアン オイル カンパニー | Steam cracking process and system using integrated gas-liquid separation |
| EP3110922B1 (en) | 2014-02-25 | 2018-09-26 | Saudi Basic Industries Corporation | A method of controlling the supply and allocation of hydrogen gas in a hydrogen system of a refinery integrated with olefins and aromatics plants |
| EP3110919B1 (en) * | 2014-02-25 | 2018-05-16 | Saudi Basic Industries Corporation | Process for producing btx from a mixed hydrocarbon source using pyrolysis |
| EP3484980A1 (en) * | 2016-07-13 | 2019-05-22 | SABIC Global Technologies B.V. | A process which does simultaneous dehydrochlorination and hydrocracking of pyrolysis oils from mixed plastic pyrolysis while achieving selective hydrodealkylation of c9+ aromatics |
| US11168271B2 (en) | 2017-02-02 | 2021-11-09 | Sabic Global Technologies B.V. | Integrated hydrotreating and steam pyrolysis process for the direct processing of a crude oil to produce olefinic and aromatic petrochemicals |
| EA038032B1 (en) * | 2017-02-02 | 2021-06-25 | Сабик Глоубл Текнолоджиз Б.В. | Integrated hydroprocessing, steam pyrolysis and resid hydrocracking process for direct conversion of crude oil to produce olefinic and aromatic petrochemicals |
| WO2018142351A1 (en) * | 2017-02-02 | 2018-08-09 | Sabic Global Technologies B.V. | A process for the preparation of a feedstock for a hydroprocessing unit and an integrated hydrotreating and steam pyrolysis process for the direct processing of a crude oil to produce olefinic and aromatic petrochemicals |
| EP3655504A1 (en) * | 2017-07-17 | 2020-05-27 | Saudi Arabian Oil Company | Systems and methods for processing heavy oils |
| US11167239B2 (en) * | 2018-09-28 | 2021-11-09 | Uop Llc | Pressure swing adsorption integration in steam cracking ethylene plants for improved hydrogen recovery |
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- 2013-01-27 KR KR1020147024068A patent/KR102071654B1/en active IP Right Grant
- 2013-01-27 CN CN201710589272.3A patent/CN107216914B/en active Active
- 2013-01-27 EP EP19207001.9A patent/EP3633013A1/en active Pending
- 2013-01-27 SG SG11201404386WA patent/SG11201404386WA/en unknown
- 2013-01-27 WO PCT/US2013/023336 patent/WO2013112969A2/en active Application Filing
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Also Published As
| Publication number | Publication date |
|---|---|
| EP2807237B1 (en) | 2019-11-06 |
| EP2807237A2 (en) | 2014-12-03 |
| SG11201404386WA (en) | 2014-11-27 |
| EP3633013A1 (en) | 2020-04-08 |
| JP2017201020A (en) | 2017-11-09 |
| KR20140138142A (en) | 2014-12-03 |
| JP6606121B2 (en) | 2019-11-13 |
| CN107216914B (en) | 2020-02-21 |
| WO2013112969A3 (en) | 2013-11-07 |
| CN107216914A (en) | 2017-09-29 |
| JP6151717B2 (en) | 2017-06-21 |
| JP2015509127A (en) | 2015-03-26 |
| KR102071654B1 (en) | 2020-01-30 |
| CN104093821A (en) | 2014-10-08 |
| WO2013112969A2 (en) | 2013-08-01 |
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