阅读说明：本技术 改善重油管道运输效率的方法 (Method for improving transportation efficiency of heavy oil pipeline ) 是由 R·P·霍奇金斯 O·R·柯塞奥卢 于 2020-02-21 设计创作，主要内容包括：二硫化物油(DSO)化合物(作为烃精炼原料的硫醇氧化的副产物而回收)及它们的氧化衍生物氧化二硫化物油(ODSO)作为稀释剂可有效降低粘度,从而改善重油(特别是井口原油)的管道运输性能。使用DSO和/或ODSO化合物作为稀释剂将原本价值极低的废油产品转化为有价值的商品,可用于改善特别是油田管道应用中的重油的运输性能。(Disulfide oil (DSO) compounds, recovered as a byproduct of mercaptan oxidation of hydrocarbon refinery feedstocks, and their oxidized derivatives, oxidized disulfide oil (ODSO), as a diluent, are effective in reducing viscosity, thereby improving pipeline transport properties of heavy oils, particularly well head crude oils. The use of DSO and/or ODSO compounds as diluents converts the otherwise extremely low value waste oil products into valuable commodities useful for improving the transport properties of heavy oils, particularly in oilfield pipeline applications.)

1. A process for reducing the viscosity of a heavy oil feedstream, wherein the process comprises mixing the heavy oil feedstream with a predetermined amount of a liquid hydrocarbon diluent in at least one mixing zone to produce a heavy oil-diluent blend;

the liquid hydrocarbon diluent is selected from the group consisting of: one or more DSO compounds, one or more ODSO compounds, or a combination thereof,

the heavy oil-diluent blend has a lower density and lower viscosity than the heavy oil feedstream, the DSO compound and the ODSO compound are derived from mercaptan oxidation of a hydrocarbon refinery feedstock.

2. The process of claim 1 wherein the liquid hydrocarbon diluent is one or more disulfide oil compounds having the general formula:

R'SSR

wherein R and R 'are saturated or unsaturated, linear, branched or cyclic hydrocarbons having 1, 2, 3 and up to 10 or more carbon atoms, and R' may be the same or different.

3. The process of claim 1 wherein the liquid hydrocarbon diluent is one or more oxygenated disulfide oil compounds having the general formula:

O_xR'SSR

wherein x is an integer of 1 to 4, R and R 'are saturated or unsaturated, linear, branched or cyclic hydrocarbons having 1, 2, 3 and up to 10 or more carbon atoms, and R' may be the same or different.

4. The process of claim 1 wherein the liquid hydrocarbon diluent is one or more oxygenated disulfide oil compounds having the general formula:

O_xRSSOH

wherein x is 2, 3 or 4, and R may be a saturated or unsaturated, linear, branched or cyclic hydrocarbon having 1, 2, 3 and up to 10 or more carbon atoms.

5. The process according to any of the preceding claims, wherein the heavy oil is selected from the group consisting of: crude oil recovered at the wellhead, bitumen, heavy crude oil, coal-derived oil, atmospheric resid, vacuum resid, bitumen from solvent deasphalting, and heavy oil derived from refining processes such as distillation, solvent deasphalting, delayed coking, or FCC processing.

6. The process of any of the preceding claims, wherein the heavy oil-diluent blend is transported from the at least one mixing zone to a transport pipeline.

7. The process of any preceding claim, wherein the heavy oil-diluent blend comprises from 1W% to 99W% diluent, based on the total weight of the blend.

8. The process of any preceding claim, wherein the heavy oil-diluent blend comprises from 5 to 50W% diluent based on the total weight of the blend.

9. A process according to any one of the preceding claims, wherein the initial viscosity of the heavy oil at 50 ℃ is at least 1000 mPa-s.

10. The process of any of the preceding claims, wherein the heavy oil-diluent blend has a viscosity of less than or equal to 380 mPa-s under conditions in a transport pipeline.

11. The method of claim 10, wherein the heavy oil-diluent blend has a viscosity of less than 200 mPa-s.

12. The process of any of the preceding claims wherein the heavy oil has an API gravity of less than or equal to 30 °.

13. A method of reducing the viscosity of a heavy oil feedstream transported in a petroleum pipeline, wherein the method comprises:

a. mixing a heavy oil feedstream with a predetermined amount of fresh liquid hydrocarbon diluent in a mixing zone at a first location to produce a heavy oil-diluent blend having a lower density and lower viscosity than the heavy oil feedstream alone,

wherein the fresh diluent stream comprises one or more DSO compounds, one or more ODSO compounds, or a combination thereof, the DSO compounds and ODSO compounds derived from the mercaptan oxidation of a refinery feed stream;

b. recovering the heavy oil-diluent blend from the mixing zone at a first location as a product stream;

c. the recovered heavy oil-diluent blend product stream is introduced into a first transport conduit for transport to a second location.

14. The method of claim 13, wherein the method further comprises the steps of:

d. receiving the heavy oil-diluent blend of step (c) at a second location, introducing the blend into a fractionation zone, separating the heavy oil from the diluent;

e. recovering the liquid hydrocarbon diluent; and

f. the heavy oil is recovered or further processed as a product stream.

15. The method of claim 13 or 14, wherein the heavy oil-diluent blend is free or substantially free of precipitates.

16. The method of any of claims 13, 14 or 15, wherein the heavy oil is a wellhead crude oil.

17. The method of claim 14, wherein the method further comprises the steps of:

g. introducing the diluent recovered in step (e) into a second transport conduit, returning the diluent to the first location as a recycle diluent stream; and

h. the recycle diluent stream and fresh diluent are introduced to mix with the heavy oil, producing a heavy oil-diluent blend.

18. The process of claim 14 wherein the heavy oil stream is further processed in a fractionation zone at the second location to yield more than one feed for downstream refining operations.

19. The method of claim 6, wherein the heavy oil-diluent blend delivered to a transport pipeline is at a temperature of 20 ℃ to 80 ℃ and a pressure of 1 bar to 5 bar.

Technical Field

The present disclosure relates to pipeline transportation of heavy oils, and in particular to improving transportation efficiency by reducing the viscosity of heavy oils.

Background

Transporting oil through pipelines

Oil transport via pipelines is becoming an increasingly complex and technical process, especially in view of the energy required in the field of transporting heavy, highly viscous crude oil from well heads. Heavy crude oils are generally highly viscous and can have solids-like properties at room temperature. This means that they are not easily pumped through pipelines, which is necessary to transport oil from the wellhead to refineries or pre-treatment stations, such as gas/oil separation plants. Since a significant portion of the global oil reserves includes heavy crude oil, both oil field producers and refineries are particularly concerned with techniques for increasing pipeline transport efficiency as a means of reducing associated energy costs.

The viscosity of heavy oils can exceed values of 100,000 mPa-s, while the preferred viscosity for effective transport of fluids in pipelines is typically less than 380 mPa-s. Jos E A.D.Jorge Antheyta and Luis C.The properties of the various crudes are compared in summary in Table 1 of Required Viscosity Values to Enterure Performance transport of cloud Oil, Energy Fuels 2016, 30, 8850-8854 (which is incorporated herein by reference in its entirety).

TABLE 1

From the data shown in table 1, it is clear that the viscosity may vary significantly depending on the crude oil source and is not directly dependent on the API gravity of the oil. The data in table 1 also illustrates the relationship between viscosity and temperature. As known to those skilled in the art, wellhead crude oil temperatures can vary widely (e.g., between subsea and land-based production facilities), and to reduce the viscosity of the mixture in the production tubing, light oil has been introduced into the well annulus (annulus).

Also, in the same manner as above,crude oils are classified into the following four categories according to viscosity at 25 ℃:

group a is medium heavy crude oil with viscosity of 10 to 100cP (equivalent to 10 to 100mPa · s, also equivalent to about 11 to 111 cSt);

class B is a very heavy crude oil with a viscosity of 100 to 10,000cP (equivalent to 100 to 10,000mPa · s, also equivalent to about 111 to 10,150 cSt);

group C is bitumen with a viscosity greater than 10,000cP (corresponding to 10,000 mPa.s, also corresponding to about 10,150 cSt). Class C oils typically have an API gravity of less than 7 °, meaning that they are immobile under reservoir conditions, and therefore require thermal recovery methods (e.g., steam injection thermal recovery) or recovery using mining techniques; and

class D is bituminous shale, which is considered a source rock that can be extracted using mining or in situ techniques.

With the worldwide depletion of light and medium oil reserves, the production of abundant heavy crude oil is becoming a more popular source of refinery feedstock. Various techniques are known for reducing the viscosity of heavy oils. These techniques are generally classified into the following categories: (a) viscosity reduction, including techniques such as dilution/blending, heating, emulsification, and pour point reduction; (b) reducing friction, including the step of adding a drag reducing additive; (c) upgrading (upgrading), including processes for producing synthetic crude oils having lower viscosities.

Common diluents used to reduce viscosity include natural gas condensate, naphtha, kerosene and lighter crude oils. In addition, alcohols and ethers (i.e., polar solvents) may also be used, which may actually increase the octane number of downstream products. The amount of diluent required to treat heavy crude oil is typically up to 20W%, whereas 25 to 50W% diluent is required to treat heavier classes of oil (e.g. bitumen).

The viscosity of heavy crude oil can also be reduced by an order of magnitude by heating the oil and/or the pipeline, thereby improving the effective flow of the oil. However, heating or preheating of oil and/or pipelines can generate substantial capital and operating costs associated with infrastructure and energy consumption, and can also carry the risk of potential pipeline corrosion and associated environmental problems.

Surfactants can be used to emulsify and stabilize petroleum in water to reduce the viscosity of the petroleum. In this method, the surfactant is located at the oil-water interface and hinders droplet growth and phase separation. Crude oils naturally contain components that can act as emulsifiers, such as asphaltenes, porphyrins, resins, and naphthenic acids. However, if emulsification is used to reduce the viscosity of the oil for transportation, the oil-water emulsion must be broken in a gas/oil separation station (GOSP). Thermal, electrical, and chemical demulsification techniques in combination with solvent addition or pH change can be used to disrupt the emulsification. The rheology of the emulsion depends to a large extent on the size and distribution of the droplets, which is related to the choice of surfactant and the process conditions. Crude oils are generally stable when the droplet size is below 10 μm. Disadvantages of this approach include: the cost associated with surfactants, the degree to which the surfactant can retain the emulsion during shipping, and the need to remove the surfactant from the emulsion during refining.

Crude oil comprises liquid phase maltenes (maltenes), i.e., saturated hydrocarbons, aromatic hydrocarbons, resins, and solute asphaltenes. The precipitation and aggregation of asphaltenes in colloidal suspensions results in high density and high viscosity. Pour point is the lowest temperature at which the oil stops flowing and crystals may form. Polymerization inhibitors (e.g., polyacrylates and polymethacrylates) can be used to minimize crystal formation/deposition and improve crude oil flow characteristics.

Wall friction and viscous drag of the pipeline during crude oil transportation are significantly more pronounced when transporting heavy crude oil than when transporting lighter oil. Viscous drag is a result of shear stress on the wall fluid, resulting in a reduction in fluid pressure within the pipe. Drag reduction may be achieved by lubricating the inner wall of the conduit.

Upgrading of oils typically involves thermally cracking and catalytically processing them to produce synthetic oils with reduced viscosity and improved flow characteristics. For example, visbreaking technology has been widely accepted and devices for reducing the viscosity of heavy oils are installed around the world. Upgrading heavy oil at a wellhead is not always economically feasible, and the availability of diluents is a logistical problem that refineries must address when planning pipeline transportation to downstream processing facilities.

There are the following problems: an efficient and economical method is provided to reduce viscosity and thereby improve the transport properties of heavy oils.

Mercaptan oxidation (MEROX) process

Mercaptan oxidation processes, commonly referred to as the MEROX process, have long been used to remove mercaptans (which typically have a foul odor) found in many hydrocarbon streams, and were introduced into the refining industry more than fifty years ago. For environmental reasons, regulatory requirements reduce the sulfur content of fuels, and refineries have and will continue to face the problem of handling the large amounts of sulfur-containing byproducts produced in mercaptan oxidation processes.

Disulfide oil (DSO) compounds are produced as a byproduct of the MEROX process in which mercaptans are removed from any of a variety of petroleum streams, including liquefied petroleum gas, naphtha, and other hydrocarbon fractions. It is commonly referred to as a "saccharification process" because it removes sour or malodorous mercaptans present in the crude oil. For convenience, the term "DSO" is used in the specification and claims and should be understood to include mixtures of disulfide oils produced as a byproduct of the mercaptan oxidation process.

As mentioned above, the name "MEROX" derives from the function of the process itself, namely the conversion of mercaptans by oxidation. The MEROX process is based in all its applications on the ability of organometallic catalysts to accelerate the oxidation of mercaptans to disulfides in an alkaline environment (e.g., caustic) at near ambient temperature and pressure. The overall reaction can be expressed as follows:

RSH+1/4O₂→1/2RSSR+1/2H₂O (1)

in the formula, R is a hydrocarbon chain, which may be linear, branched or cyclic, and which may be saturated or unsaturated. Most petroleum fractions will have a mixture of mercaptans and so R can have 1, 2, 3 and up to more than 10 carbon atoms in the chain. In the reaction, the length of the variable chain is determined by R and R'. The reaction was then written as:

2R'SH+2RSH+O₂→2R'SSR+2H₂O (2)

this reaction occurs spontaneously when any sour, thiol-containing distillate is exposed to atmospheric oxygen, but at a very slow rate. In addition, the catalytic reaction (1) described above requires the presence of an alkaline caustic solution, such as an aqueous sodium hydroxide solution. Mercaptan oxidation proceeds at an economically practical rate at moderate refinery downstream temperatures.

The MEROX process can be performed on both a liquid stream and a combined gas stream and liquid stream. In the case of a liquid stream, the mercaptans are directly converted to disulfides which remain in the product, so that the total sulfur content of the effluent stream is not reduced.

The MEROX process typically uses a fixed bed reactor system to treat the liquid stream and is typically used for feed stocks (charge stocks) ending above 135 ℃ to 150 ℃. Mercaptans are converted to disulfides in a fixed bed reactor system over a catalyst (e.g., activated carbon impregnated with a MEROX reagent), and the mercaptans are wetted with a caustic solution. Air is injected into the hydrocarbon feedstream prior to the reactor and the mercaptans in the feed are oxidized to disulfides as they pass through the catalyst impregnated bed. The disulfides are substantially insoluble in caustic and remain in the hydrocarbon phase. Post-treatment is required to remove the known side reactions (e.g. H)₂Neutralization of S, oxidation of phenolic compounds, entrained caustic, etc.).

The vapour pressure of disulfides is relatively low compared to that of mercaptans, so that disulfides are much less objectionable in terms of odor; however, due to the sulphur content, disulfides are environmentally unacceptable and disposal of the disulfides can be problematic.

In the case of a mixed gas stream and liquid stream, two phases of the hydrocarbon stream are extracted. The completeness of mercaptan extraction depends on the solubility of the mercaptan in the alkaline solution, which depends on the individual mercaptan molecular weight, the degree of branching of the mercaptan molecules, the caustic concentration, and the system temperature. Thereafter, the resulting DSO compounds are separated and the caustic solution is regenerated by air oxidation in the presence of the catalyst and can be reused.

Referring to the drawings, FIG. 1 is a simplified schematic diagram of a generalized conventional version of the prior art MEROX process that employs liquid-liquid extraction to remove sulfur compounds in one embodiment to treat a hydrocarbon stream (1) containing a combination of propane and butane of mercaptans comprising the steps of:

introducing a hydrocarbon stream (1) and a homogeneous cobalt-based catalyst into an extraction vessel (10) containing a caustic solution (2);

flowing the combined stream of hydrocarbon and catalyst in countercurrent fashion through an extraction section of an extraction vessel (10), the extraction section comprising one or more liquid-liquid contacting extraction plates or trays (not shown) for performing a catalytic reaction with the circulating caustic solution to convert mercaptans to water-soluble alkali metal alkane thiolate compounds;

withdrawing a hydrocarbon product stream (3) free or substantially free of mercaptans from the extraction vessel (10);

recovering a combined spent caustic and alkali metal alkanethiolate stream (4) from the extraction vessel (10);

catalytic wet air oxidation of spent caustic in reactor (20), introducing catalyst (5) and air (6) into reactor (20) to regenerate spent caustic (8) and convert alkali metal alkane thiolate compounds to disulfide oils; and

a byproduct stream (7) of disulfide oil (DSO) compounds and minor amounts of sulfides is recovered.

Preferably, the effluent of the wet air oxidation step in the MEROX process, which contains a small proportion of sulfides and a large proportion of disulfide oils, may also contain mono-and tri-sulfides. As known to those skilled in the art, the composition of this effluent stream depends on the effectiveness of the MEROX process, assuming that the sulfide is a carryover material. A variety of catalysts have been developed for commercial practice of this process. The efficiency of the MEROX process also depends on the presence of dissolved H in the treated feed stream₂The amount of S. Performing a prewash step to remove dissolved H₂S is a common operation of a refinery.

The disulfide oil compounds produced in the MEROX process can contain various disulfides. For example, a MEROX unit designed to recover propane and butane produced a mixture of disulfide oils with compositions listed in Table 2:

TABLE 2

Table 2 shows the composition of the disulfide oils from the semi-quantitative GC-MS data. Although the components were not measured according to the standard, the data representing the relative amounts in table 2 are accurate. Quantitative total sulfur content was determined by energy dispersive X-ray fluorescence spectroscopy, indicating 63 wt% sulfur, which value will be used in subsequent calculations. The GC-MS results provide evidence of trace trisulfide content; however, most disulfide oil streams contain the three components identified in table 2.

The byproduct disulfide oil produced by the MEROX unit can be processed and/or disposed of in various other refining operations. For example, DSO can be added to the fuel oil pool at the expense of higher sulfur content in the pool. DSO can be processed in a hydrotreating/hydrocracking unit, but at the expense of higher hydrogen consumption. Disulfide oils also have an unpleasant malodorous or sour taste, which is relatively less intense because of its relatively low vapor pressure at ambient temperatures; however, the disposal of such oils is problematic.

Disulfide oil (DSO) compounds, by-products from mercaptan oxidation processes, can be oxidized, preferably in the presence of a catalyst, and constitute a rich source of ODSO compounds (sulfoxides, sulfonates, sulfinates, and sulfones). The oxidizing agent may be a liquid peroxide selected from the group consisting of: alkyl hydroperoxides, aryl hydroperoxides, dialkyl peroxides, diaryl peroxides, peresters, and hydrogen peroxide. The oxidant may also be a gas, including air, oxygen, ozone, and nitrogen oxides. The catalyst is preferably a homogeneous water-soluble compound which is an active-material-containing transition metal selected from the group consisting of: mo (VI), W (VI), V (V), Ti (IV) and combinations thereof.

ODSO compounds have been found to be useful as lubricity additives for diesel fuels, which are more economical than the additives currently used for this purpose, and also as solvents for aromatic solvent extraction processes. If a refinery has produced or inventoried an amount of ODSO compound already in stock that exceeds the foreseeable needs of these or other uses, the refinery may wish to dispose of the ODSO compound to clean storage vessels and/or to remove the product from inventory for tax reasons.

Thus, there are clear and long-felt needs as follows: identifying new uses for relatively large quantities of DSO refinery by-products in mercaptan oxidation processes (which can bring about economic benefits associated with refinery operations and elsewhere); as well as increasing the value of such by-products to the refinery operator.

Disclosure of Invention

The above needs are met and other advantages are provided by the present process which advantageously utilizes relatively low value disulfide oils and their derivatives (oxidized disulfide oils) to reduce viscosity, thereby improving pipeline transport characteristics of heavy oils. The disulfide oils and oxidized disulfide oils used as viscosity modifiers for heavy crude oils and other viscous hydrocarbons in the process and system of the present invention are by-products of the mercaptan oxidation process from refinery feedstocks.

In one embodiment, the present disclosure relates to an integrated refining process for modifying properties (including viscosity and density) of heavy oil using DSO compounds (produced from the removal of mercaptans from a hydrocarbon stream containing mercaptans) before and/or during the transportation of the heavy oil in a pipeline. The integration method comprises the following steps:

introducing a hydrocarbon stream containing mercaptans to an extraction vessel containing a basic solution;

passing the hydrocarbon stream through an extraction section of an extraction vessel, the extraction section comprising one or more liquid-liquid contacting plates, to effect a reaction to convert mercaptans to water soluble compounds;

withdrawing a mercaptan-free hydrocarbon product stream from the extraction vessel;

recovering a spent caustic solution containing sulfur compounds from the extraction vessel;

air oxidizing a sulfur-containing spent caustic solution to produce a wastewater and a byproduct stream containing disulfide oils and sulfides;

separating disulfide oil and sulfides from the wastewater;

recovering disulfide oil (DSO) and determining the viscosity of the disulfide oil (DSO) under standard test conditions; and

a predetermined amount of a disulfide oil (DSO) stream is mixed with a heavy oil stream of known viscosity to produce a heavy oil-DSO blend, wherein the heavy oil-DSO blend has a lower density and a lower viscosity than the heavy oil stream under prevailing conditions.

Suitable test methods for determining the viscosity of the DSO stream include ASTM D445, ASTM D466 and ASTM D7042.

It is to be understood that since the source of the DSO is a refinery feedstream, the "R" and "R '" hydrocarbon substituents in the formula R' SSR can vary, such as methyl, ethyl, and other subgroups containing up to 10 carbon atoms, and the number of sulfur atoms S in the received DSO feedstream is up to 3, i.e., trisulfide compounds. Similar conditions exist in embodiments utilizing oxidized derivatives of DSO byproducts (i.e., embodiments utilizing ODSO streams or mixed streams of DSO/ODSO compounds).

The methods and apparatus of the present disclosure enable refineries and natural gas processing plant operators to utilize relatively low value by-products, which some refineries may treat as disulfide oil waste streams, to advantageously reduce the viscosity and density of heavy oils to facilitate transport of the heavy oils through pipelines, or to reduce the viscosity to facilitate processing within the refinery battery limits.

The use of diluents as viscosity modifiers for hydrocarbons is known in the art. The preliminary step involves determining the viscosity of at least the heavy oil and the diluents DSO and ODSO compounds under predetermined conditions (including in particular temperature and pressure) prevailing in the pipeline.

It is to be understood that the amount of diluent DSO compound (i.e., in volume% or weight%) is predetermined to achieve a reduction in the viscosity of the heavy oil-diluent blend to a desired value to achieve a desired degree of enhancement in pipeline transport efficiency under the prevailing conditions of a given pipeline section. It will also be appreciated by those skilled in the art that heavy oil moving in a pipeline is expected to experience changes in temperature and pressure as it moves from the wellhead to the initial processing location through hundreds of miles of pipeline. Climate changes (e.g., extreme heat and cold between day and night in high desert areas, and greater seasonal fluctuations during summer and winter) will affect the temperature and pressure of heavy oil transported through pipelines.

In the following description, for convenience, the terms "disulfide oil", "disulfide-containing oil", "DSO mixture" and "DSO compound" are used interchangeably and will be understood to include a variety of compounds during the oxidation of the feed mercaptans, the proportions of which vary with the nature and source of the feed from which they are derived.

In the following description, for convenience, the terms "oxidized disulfide oil", "oxidized disulfide containing oil", "derivative of disulfide oil", "ODSO mixture" and "ODSO compound" are used interchangeably and will also be understood to mean that various products are present.

In the following description, for convenience, the terms "DSO/ODSO", "DSO/ODSO mixture" and "DSO/ODSO compound" are used interchangeably.

In the following description, for convenience, the diluent may be referred to as "DSO"; it is to be understood that the term "diluent" includes ODSO alone or a combination of ODSO and DSO.

Drawings

The method of the present disclosure will be described in more detail below with reference to the attached drawing figures, wherein like reference numerals designate identical or similar elements, and wherein:

FIG. 1 is a simplified schematic of a generalized version of the prior art mercaptan oxidation or MEROX process for liquid-liquid extraction of a combined propane and butane stream;

FIG. 2 is a simplified schematic diagram of one embodiment of the disclosed method; and

FIG. 3 is a graph showing the reduction in viscosity of heavy oil after addition and mixing of DSO (recovered from a refinery mercaptan oxidation process).

Detailed Description

Referring now to fig. 2, the method and system of the present disclosure includes: a mixing zone (110) and a first transport zone (130), and optionally a fractionation zone (150) and a second transport zone (170). A DSO stream (recovered as a by-product of mercaptan oxidation of a hydrocarbon refinery feedstock) and/or an ODSO stream or mixed DSO/ODSO compound is used as a diluent stream. At a first location, a fresh diluent stream (102) and a heavy oil stream (112) are introduced into a mixing zone (110) to mix, producing a heavy oil-diluent blend (116). The heavy oil-diluent blend (116) is introduced into a first transport zone (130) for transport to a second location, such as a GOSP or refinery. The heavy oil-diluent blend (134) reaching the second location is unchanged relative to the heavy oil-diluent blend (116) passing from the mixing zone. It should be understood that the term "transportation area" includes conventional petroleum pipelines and/or piping systems. Including collection conduits extending from multiple wellheads in an oilfield to one or more local/regional storage tanks, and long distance conduits from the wellheads to a processing facility.

The heavy oil-diluent blend (134) may optionally be sent to a fractionation zone (150) for separation into a heavy oil stream (152) and a recovered diluent stream (154). The diluent stream (154) may be discharged as stream (158) for disposal or, preferably, the diluent stream (154) is recovered as a DSO recycle stream (156) and conveyed to the second transport zone (170) to be returned as a DSO recycle stream (176) at a first location where it is mixed with the fresh diluent stream (102) upstream of the mixing zone (110) to the first location. In certain embodiments, up to 90W% or 95W% or even 99W% of the DSO introduced as fresh diluent stream (102) is recovered as a DSO recycle stream (176). In another embodiment (not shown), the DSO recycle stream (156) is sent to another location for further use.

The heavy oil stream (152) may be conventionally processed in downstream refining operations.

In certain embodiments, the second transport area (170) is eliminated. In this embodiment, a separate conduit is used within the first transport zone (130) to convey the DSO recycle stream (156) so that it does not mix with the heavy oil-diluent blend.

In embodiments where the heavy oil-diluent blend (134) is not processed in the fractionation zone (150) to recover DSO, the blend is conventionally processed in a downstream refining operation (not shown) at the second location.

The fractionation zone (150) may include a flash drum, a distillation column, a stripping column (operated with steam or nitrogen or a combination thereof), or other fractionation devices known in the art.

Examples of suitable feeds that make up the heavy oil stream (112) include: crude oil, bitumen, heavy crude oil, coal produced oil (coal liquid), atmospheric residuum (atmospheric residue), vacuum residuum (vacuum residue), bitumen from solvent deasphalting, and heavy oils derived from refinery processes (e.g., distillation, solvent deasphalting, delayed coking, FCC processing) produced at well heads. Suitable feeds include crude oils of the class a, class B and class C categories as defined above.

In certain embodiments, the heavy oil has an API gravity of less than 30 °, less than 20 °, or less than 10 °. In certain embodiments, the viscosity of the heavy oil is greater than about 1,000 mPa-s, and in preferred embodiments, the viscosity of the heavy oil is greater than about 380 mPa-s.

The DSO, ODSO or mixed DSO/ODSO diluent stream is mixed with a predetermined amount of heavy oil of 1 to 99W% (preferably 5 to 50W%). The diluent stream is compatible with asphaltenes and therefore does not form a precipitate when mixed with heavy oil.

In certain embodiments, the composition as set forth in Hart, a., j.petrol explorer.prod.technol.2014, 4: 327 (which is incorporated herein by reference in its entirety), the heavy oil-diluent blend has a viscosity of less than about 400 mPa-s, less than about 380 mPa-s, or less than about 200 mPa-s.

In certain embodiments, the heavy oil-diluent blend is transported in a pipeline at a temperature of 20 ℃ to 80 ℃, or at a temperature of 20 ℃ to 80 ℃ and a pressure of 1 bar to 5 bar.

Downstream refinery operations include, but are not limited to, gas/oil separation stations, processes such as distillation, naphtha hydrotreating, kerosene hydrotreating, diesel hydrotreating, and hydrocracking operations.

In certain embodiments, the diluent stream is comprised of one or more disulfide oil compounds of the general formula R ' SSR, where R and R ' are saturated or unsaturated straight, branched or cyclic hydrocarbons having 1, 2, 3 and up to 10 carbon atoms, and R ' may be the same or different.

In other embodiments, the diluent stream is formed from more than one stream having the general formula O_xOxidative disulfide oiling of R' SSRThe composition is characterized in that x is an integer of 1 to 4, R and R 'are saturated or unsaturated straight-chain, branched or cyclic hydrocarbons with 1, 2, 3 and more than 10 carbon atoms, and R' can be the same or different.

Other compounds formed in the mixture of oxidized disulfide oil compounds may have the structure O_xRSSOH, wherein x is 2, 3 or 4 and R may be a saturated or unsaturated, linear, branched or cyclic hydrocarbon having 1, 2, 3 and up to 10 or more carbon atoms.

Table 3 includes polar and water soluble ODSO compounds, as well as non-polar and water insoluble ODSO compounds. ODSO compounds containing 1 and 2 oxygen atoms are non-polar and water-insoluble. ODSO compounds containing more than 3 oxygen atoms are water soluble. The generation of polar or non-polar ODSO compounds depends in part on the reaction conditions during oxidation. The structures of some of the compounds in table 3 are given by: experiment of oxidizing DSO mixture¹³And comparing the C-135-DEPT-NMR spectrum with a stored preset spectrum database to obtain the closest corresponding relation.

TABLE 3

As will be understood by those skilled in the art, the temperature of the heavy crude oil at the wellhead may be from-45 ℃ to 120 ℃ or 150 ℃ or even up to 200 ℃, and will exhibit a much lower initial viscosity. The thermally produced crude oil may be introduced into a pipeline for long distance transport to a remote GOSP and/or refinery or for transfer to an oil storage tank at elevated temperatures. Depending on the season and well head location and the GOSP, refinery or other storage or processing facility, the crude oil will experience a calculable decrease in temperature with an increase in viscosity, which will result in an increase in the energy required to transport the heavy oil through the transport pipeline and a corresponding decrease in the overall efficiency of the transport.

In one embodiment of the present methods and systems, a stream of DSO diluent is introduced into the pipeline at a predetermined location along the transport path in a predetermined amount, thereby increasing the total weight percent of DSO diluent in the heavy oil to periodically or intermittently reduce the viscosity of the heavy oil-diluent blend as it passes through the pipeline. It is well known from fluid mechanics that when heavy oil undergoes a change in direction, turbulence and associated energy losses due to friction occur at pipe bends and joints. The addition of the DSO diluent can further reduce the viscosity upstream of a section of the pipeline in which the flow path of the heavy oil will undergo significant changes, thereby creating turbulence, which can be used to increase the efficiency of the transfer through the turbulent zone.

Additional savings may be realized if the DSO diluent is recovered and recycled to multiple diluent addition stations (located intermediate the wellhead or first addition station and the GOSP or refinery) where the DSO diluent is recovered separately from the heavy oil and piped back to more than one intermediate addition station for use as recycle diluent.

Similarly, additional DSO diluent may be added to the transport heavy oil flowing in the pipeline due to temperature reduction (i.e., heat transfer loss through the pipeline walls) due to cooling at prevailing ambient conditions. Adding DSO diluent at geographically separated predetermined locations along a generally straight pipeline (traversing distances above hundreds of miles) will enable the viscosity of the blended stream to be maintained at a desired viscosity or range of viscosities. The diluent may also be advantageously added to the pipeline at an intermediate location between the wellhead and the oilfield storage tank and between the storage tank and the GOSP or refinery, where the heavy oil flowing therethrough undergoes a significant temperature reduction. The use of an intermediate addition station may save on the volume of DSO diluent needed to maintain the desired viscosity throughout the length of the pipeline. Costs may also be saved since only a portion of the recycled diluent is transported to the initial injection point at the far end of the pipeline.

It will be apparent to those of ordinary skill in the art that the use of more than one intermediate addition station will require: a recycle diluent storage tank, a pump, a dedicated recycle transport pipeline, means for mixing and/or injecting diluent into the heavy crude oil, and associated control equipment and facilities. Conventional and routine cost-effective calculations may be applied to determine the number and location of intermediate add stations.

In certain embodiments (not shown), the DSO diluent is simply mixed with the heavy oil stream to reduce the viscosity of the heavy oil to facilitate pipeline transportation for processing within the refinery battery-limits.

Example 1

The viscosities of samples of the vacuum resid and DSO diluent (recovered as a by-product of mercaptan oxidation of a hydrocarbon refinery feedstock) were measured at 37.7 ℃ and were 31,116mPa · s and 0.61mPa · s, respectively. The properties and composition of the DSO are seen in table 2. Blending calculations were performed on the vacuum resid-DSO diluent stream and the results are shown in fig. 3, where simulated viscosity data for a heavy oil-diluent blend is a function of DSO diluent content in the blend. The results show that when the blend contains 20V% DSO diluent, the viscosity of the blend is sufficiently reduced to meet the pipe specification of <380mPa · s.

As can be appreciated from the above description, the disclosed process provides a cost effective and environmentally acceptable basis for turning byproduct disulfide oils and their oxidized DSO derivatives to beneficial uses.

The process of the present invention has been described above and in the accompanying drawings; modifications and variations of the described methods will be apparent to those of ordinary skill in the art in light of the present description, and the scope of protection is to be determined by the appended claims.