CA3022709C - Analyzing bitumen containing streams - Google Patents

Analyzing bitumen containing streams Download PDF

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CA3022709C
CA3022709C CA3022709A CA3022709A CA3022709C CA 3022709 C CA3022709 C CA 3022709C CA 3022709 A CA3022709 A CA 3022709A CA 3022709 A CA3022709 A CA 3022709A CA 3022709 C CA3022709 C CA 3022709C
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Payman Esmaeili
Asfaw Bekele
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ExxonMobil Upstream Research Co
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
    • G01N23/223—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00—Working-up pitch, asphalt, bitumen
    • C10C3/08—Working-up pitch, asphalt, bitumen by selective extraction
    • 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
    • C10G1/045—Separation of insoluble materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/24—Earth materials
    • G01N33/241—Earth materials for hydrocarbon content
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2223/00—Investigating materials by wave or particle radiation
    • G01N2223/60—Specific applications or type of materials
    • G01N2223/616—Specific applications or type of materials earth materials

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
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  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
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  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Food Science & Technology (AREA)
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  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

Disclosed is a method comprising measuring a sulfur content in a bitumen containing stream using X-Ray Fluorescence (XRF), optionally estimating a bitumen content in the bitumen containing stream using generated data, comparing the sulfur content or the bitumen content to a predetermined reference range, and adjusting a process parameter, if necessary, based on the sulfur content or the bitumen content as compared to the predetermined reference range.

Description

ANALYZING BITUMEN CONTAINING STREAMS
BACKGROUND
Field of Disclosure [0001] The disclosure relates generally to the field of oil sand processing.
Description of Related Art
[0002] This section is intended to introduce various aspects of the art, which may be associated with the present disclosure. This discussion is believed to assist in providing a framework to facilitate a better understanding of particular aspects of the present disclosure.
Accordingly, it should be understood that this section should be read in this light, and not necessarily as admissions of prior art.
[0003] Modern society is greatly dependent on the use of hydrocarbon resources for fuels and chemical feedstocks. Hydrocarbons are generally found in subsurface formations that can be termed "reservoirs". Removing hydrocarbons from the reservoirs depends on numerous physical properties of the subsurface formations, such as the permeability of the rock containing the hydrocarbons, the ability of the hydrocarbons to flow through the subsurface formations, and the proportion of hydrocarbons present, among other things. Easily harvested sources of hydrocarbons are dwindling, leaving less accessible sources to satisfy future energy needs. As the costs of hydrocarbons increase, the less accessible sources become more economically attractive.
[0004] Recently, the harvesting of oil sand to remove heavy oil has become more economical. Hydrocarbon removal from oil sand may be performed by several techniques. For example, a well can be drilled to an oil sand reservoir and steam, hot air, solvents, or a combination thereof, can be injected to release the hydrocarbons. The released hydrocarbons may be collected by wells and brought to the surface. In another technique, strip or surface mining may be performed to access the oil sand, which can be treated with water, steam or solvents to extract the heavy oil.
[0005] Oil sand extraction processes are used to liberate and separate bitumen from oil sand so that the bitumen can be further processed to produce synthetic crude oil or mixed with diluent to form "dilbit" and be transported to a refinery plant. Numerous oil sand extraction processes have been developed and commercialized, many of which involve the use of water as a processing medium. Where the oil sand is treated with water, the technique may be referred to as water-based extraction (WBE). WBE is a commonly used process to extract bitumen from mined oil sand. Other processes are non-aqueous solvent-based processes. An example of a solvent-based process is described in Canadian Patent Application No.
2,724,806 (Adeyinka et al, published June 30, 2011 and entitled "Process and Systems for Solvent Extraction of Bitumen from Oil Sands"). Solvent may be used in both aqueous and non-aqueous processes.
[0006] One WBE process is the Clark hot water extraction process (the "Clark Process").
This process typically requires that mined oil sand be conditioned for extraction by being crushed to a desired lump size and then combined with hot water and perhaps other agents to form a conditioned slurry of water and crushed oil sand. In the Clark Process, an amount of sodium hydroxide (caustic) may be added to the slurry to increase the slurry pH, which enhances the liberation and separation of bitumen from the oil sand. Other WBE
processes may use other temperatures and may include other conditioning agents, which are added to the oil sand slurry, or may operate without conditioning agents. This slurry is first processed in a Primary Separation Cell (PSC), also known as a Primary Separation Vessel (PSV), to extract the bitumen from the slurry.
[0007] In one bitumen extraction process, a water and oil sand slurry is separated into three major streams in the PSC: bitumen froth, middlings, and a PSC underflow (also referred to as coarse sand tailings (CST)).
[0008] Regardless of the type of WBE process employed, the process will typically result in the production of a bitumen froth that requires treatment with a solvent.
For example, in the Clark Process, a bitumen froth stream comprises bitumen, solids, and water.
Certain processes use naphtha to dilute bitumen froth before separating the product bitumen by centrifugation.
These processes are called naphtha froth treatment (NFT) processes. Other processes use a paraffinic solvent, and are called paraffinic froth treatment (PFT) processes, to produce pipelineable bitumen with low levels of solids and water. In the PFT process, a paraffinic solvent (for example, a mixture of iso-pentane and n-pentane) is used to dilute the froth before separating the product, diluted bitumen, by gravity. A portion of the asphaltenes in the bitumen is also rejected by design in the PFT process and this rejection is used to achieve reduced solids and water levels. In both the NFT and the PFT processes, the diluted tailings (comprising water, solids and some hydrocarbon) are separated from the diluted product bitumen.
Solvent is typically recovered from the diluted product bitumen component before the bitumen is delivered to a refining facility for further processing.
[0009] The PFT process may comprise at least three units: Froth Separation Unit (FSU), Solvent Recovery Unit (SRU) and Tailings Solvent Recovery Unit (TSRU). Mixing of the solvent with the feed bitumen froth may be carried out counter-currently in two stages in separate froth separation units. The bitumen froth comprises bitumen, water, and solids. A
typical composition of bitumen froth is about 60 wt. % bitumen, 30 wt. %
water, and 10 wt. %
solids. The paraffinic solvent is used to dilute the froth before separating the product bitumen by gravity. The foregoing is only an example of a PFT process and the values are provided by way of example only. An example of a PFT process is described in Canadian Patent No.
2,587,166 to Sury.
[0010] From the PSC, the middlings, which may comprise bitumen and about 10-30 wt.
% solids, or about 20-25 wt. % solids, based on the total wt. % of the middlings, is withdrawn and sent to the flotation cells to further recover bitumen. The middlings are processed by bubbling air through the slurry and creating a bitumen froth, which is recycled back to the PSC.
Flotation tailings (FT) (also referred to as fine tailings) from the flotation cells, comprising mostly solids and water, are sent for further treatment or disposed in an external tailings area (ETA).
[0011] In ETA tailings ponds, a liquid suspension of oil sand fines in water with a solids content greater than 2 wt. %, but less than the solids content corresponding to the Liquid Limit are called Fluid Fine Tailings (FFT). FFT settle over time to produce Mature Fine Tailings (MFT), having above about 30 wt. % solids.
[0012] It would be desirable to have an alternative or improved method of analyzing a bitumen containing stream. Results of such analysis may be useful in many ways, for example to inform operation of bitumen recovery by monitoring bitumen loss in tailings, or to tune an operation based on knowledge of the ore entering the operation, to name just two.
SUMMARY
[0013] It is an object of the present disclosure to provide a method of analyzing a bitumen containing stream.
[0014] Disclosed is a method comprising measuring a sulfur content in a bitumen containing stream using X-Ray Fluorescence (XRF), optionally estimating a bitumen content in the bitumen containing stream using generated data, comparing the sulfur content or the bitumen content to a predetermined reference range, and adjusting a process parameter, if necessary, based on the sulfur content or the bitumen content as compared to the predetermined reference range.
[0015] The foregoing has broadly outlined the features of the present disclosure so that the detailed description that follows may be better understood. Additional features will also be described herein.
DETAILED DESCRIPTION
[0016] For the purpose of promoting an understanding of the principles of the disclosure, reference will now be made to the particular features and specific language will be used to describe the same. It will nevertheless be understood that no limitation of the scope of the disclosure is thereby intended. Any alterations and further modifications, and any further applications of the principles of the disclosure as described herein are contemplated as would normally occur to one skilled in the art to which the disclosure relates. It will be apparent to those skilled in the relevant art that some features that are not relevant to the present disclosure may not be shown in the drawings for the sake of clarity.
[0017] At the outset, for ease of reference, certain terms used in this application and their meaning as used in this context are set forth below. To the extent a term used herein is not defined below, it should be given the broadest definition persons in the pertinent art have given that term as reflected in at least one printed publication or issued patent.
Further, the present processes are not limited by the usage of the terms shown below, as all equivalents, synonyms, new developments and terms or processes that serve the same or a similar purpose are considered to be within the scope of the present disclosure.
[0018] Throughout this disclosure, where a range is used, any number between or inclusive of the range is implied.
[0019] A "hydrocarbon" is an organic compound that primarily includes the elements of hydrogen and carbon, although nitrogen, sulfur, oxygen, metals, or any number of other elements may be present in small amounts. Hydrocarbons generally refer to components found in heavy oil or in oil sand. However, the techniques described are not limited to heavy oils but may also be used with any number of other reservoirs to improve gravity drainage of liquids.
Hydrocarbon compounds may be aliphatic or aromatic, and may be straight chained, branched, or partially or fully cyclic.
[0020] "Bitumen" is a naturally occurring heavy oil material. Generally, it is the hydrocarbon component found in oil sand. Bitumen can vary in composition depending upon the degree of loss of more volatile components. It can vary from a very viscous, tar-like, semi-solid material to solid forms. The hydrocarbon types found in bitumen can include aliphatics, aromatics, resins, and asphaltenes. A typical bitumen might be composed of:
19 weight (wt.) % aliphatics (which can range from 5 wt. % - 30 wt. %, or higher);
19 wt. % asphaltenes (which can range from 5 wt. % - 30 wt. %, or higher);
30 wt. % aromatics (which can range from 15 wt. % - 50 wt. %, or higher);
32 wt. % resins (which can range from 15 wt. % - 50 wt. %, or higher); and some amount of sulfur (which can range in excess of 7 wt. %), the weight %
based upon total weight of the bitumen.
In addition, bitumen can contain some water and nitrogen compounds ranging from less than 0.4 wt. % to in excess of 0.7 wt. %. The percentage of the hydrocarbon found in bitumen can vary. The term "heavy oil" includes bitumen as well as lighter materials that may be found in a sand or carbonate reservoir.
[0021] "Heavy oil" includes oils which are classified by the American Petroleum Institute ("API"), as heavy oils, extra heavy oils, or bitumens. The term "heavy oil" includes bitumen. Heavy oil may have a viscosity of about 1,000 centipoise (cP) or more, 10,000 cP or more, 100,000 cP or more, or 1,000,000 cP or more. In general, a heavy oil has an API gravity between 22.3 API (density of 920 kilograms per meter cubed (kg/m3) or 0.920 grams per centimeter cubed (g/cm3)) and 10.0 API (density of 1,000 kg/m3 or 1 g/cm3).
An extra heavy oil, in general, has an API gravity of less than 10.0 API (density greater than 1,000 kg/m3 or 1 g/cm3). For example, a source of heavy oil includes oil sand or bituminous sand, which is a combination of clay, sand, water and bitumen.
[0022] "Fine particles" or "fines" are generally defined as those solids having a size of less than 44 microns (um), as determined by laser diffraction particle size measurement.
[0023] "Coarse particles" are generally defined as those solids having a size of greater than 44 microns (p.m).
[0024] The term "solvent" as used in the present disclosure should be understood to mean either a single solvent, or a combination of solvents.
[0025] The terms "approximately," "about," "substantially," and similar terms are intended to have a broad meaning in harmony with the common and accepted usage by those of ordinary skill in the art to which the subject matter of this disclosure pertains. It should be understood by those of skill in the art who review this disclosure that these terms are intended to allow a description of certain features described and claimed without restricting the scope of these features to the precise numeral ranges provided. Accordingly, these terms should be interpreted as indicating that insubstantial or inconsequential modifications or alterations of the subject matter described and are considered to be within the scope of the disclosure.
[0026] The articles "the", "a" and "an" are not necessarily limited to mean only one, but rather are inclusive and open ended so as to include, optionally, multiple such elements.
[0027] The term "paraffinic solvent" (also known as aliphatic) as used herein means solvents comprising normal paraffins, isoparaffins or blends thereof in amounts greater than 50 wt. %. Presence of other components such as olefins, aromatics or naphthenes may counteract the function of the paraffinic solvent and hence may be present in an amount of only 1 to 20 wt. % combined, for instance no more than 3 wt. %. The paraffinic solvent may be a C4 to C20 or C4 to C6 paraffinic hydrocarbon solvent or a combination of iso and normal components thereof. The paraffinic solvent may comprise pentane, iso-pentane, or a combination thereof.
The paraffinic solvent may comprise about 60 wt. % pentane and about 40 wt. %
iso-pentane, with 0- 20 wt. % of the counteracting components referred above.
[0028] A method may comprise: a) measuring a sulfur content in a bitumen containing stream using X-Ray Fluorescence (XRF); b) optionally estimating a bitumen content in the bitumen containing stream using generated data; c) comparing the sulfur content or the bitumen content to a predetermined reference range; and d) adjusting a process parameter, if necessary, based on the sulfur content or the bitumen content as compared to the predetermined reference range.
[0029] The "sulfur content" and "bitumen content" may be in any suitable unit and on any suitable basis, for instance on a weight basis. The XRF may be using any suitable XRF
device or system. Generated data means data generated using sampling of bitumen containing streams.
[0030] Step b) of estimating a bitumen content is optional because where step b) is performed, step c) compares the bitumen content to the predetermined reference range; and where step b) is not performed, step c) compares the sulfur content to the predetermined reference range.
[0031] The phrase "if necessary" in step d) simply means that if the sulfur content or the bitumen content is within the predetermined reference range, the process parameter is not adjusted.
[0032] The bitumen containing stream may be a coarse sand tailings stream (CST). The process parameter may be any suitable process parameter and may be a temperature of a bitumen extraction process producing the CST (for instance in a PSC, as described above), a caustic dosage or other extraction chemical dosage to the bitumen extraction process, an oil sand ore input rate to the bitumen extraction process, a water addition rate to the bitumen extraction process, or an oil sand ore blending ratio to the bitumen extraction process. The oil sand ore blending ratio means the ratio(s) of different oil sand ores with different compositions, which are blended. Where the sulfur content or the bitumen content is above the predetermined reference range, at least one of the following actions may be taken:
increasing the temperature of the bitumen extraction process producing the CST, increasing the caustic dosage or the other extraction chemical dosage to the bitumen extraction process, decreasing the oil sand ore input rate to the bitumen extraction process, increasing the water addition rate to the bitumen extraction process, and adjusting the oil sand ore blending ratio to the bitumen extraction process.
[0033] The bitumen containing stream may be a fine tailings stream (FT).
The process parameter may be any suitable process parameter and may be a temperature of a bitumen extraction process producing the FT (such as processing in flotation cells, as described above), a caustic dosage or other extraction chemical to the bitumen extraction process, an oil sand ore input rate to the bitumen extraction process, a middlings withdrawal rate (middlings being described above), an air flow rate to flotation cells producing the FT, a water addition rate to the bitumen extraction process producing the FT, an oil sand ore blending ratio to the bitumen extraction process producing the FT, or water addition rate to a flotation circuit to adjust for solid content. Where the sulfur content or the bitumen content is above the predetermined reference range, at least one of the following actions are taken: increasing a temperature of the bitumen extraction process producing the FT, increasing the caustic dosage or the other extraction chemical dosage to the bitumen extraction process, decreasing the oil sand ore input rate to the bitumen extraction process, decreasing the middlings withdrawal rate, increasing the air flow rate to the flotation cells producing the FT, increasing the water addition rate to the bitumen extraction process producing the FT, adjusting the oil sand ore blending ratio to the bitumen extraction process producing the FT, and adjusting the water addition rate to the flotation circuit to adjust for solid content.
[0034] The bitumen containing stream may be boiler feed water in an in-situ bitumen recovery process. The process parameter may be any suitable process parameter and may be a flotation unit efficiency parameter (e.g. gas addition rate), a hot lime softener efficiency parameter (e.g. chemical dosage), a filter efficiency parameter (e.g. using differential pressure to adjust filtration), or a weak acid cation efficiency parameter (e.g. weak acid dosage). Where the sulfur content or the bitumen content is above the predetermined reference range, at least one of the following actions may be taken: increasing the flotation unit efficiency parameter, increasing the hot lime softener efficiency parameter, increasing the filter efficiency parameter, or increasing the weak acid cation efficiency parameter.
[0035] The bitumen containing stream may be oil sand ore. The process parameter may be any suitable process parameter and may be an oil sand ore blending ratio to the bitumen extraction process, a temperature of a bitumen extraction process, a water addition rate to the bitumen extraction process, or a caustic dosage or other extraction chemical dosage to the bitumen extraction process. Where the sulfur content or the bitumen content is above or below the predetermined reference range, at least one of the following actions may be taken: adjusting the oil sand ore blending ratio to the bitumen extraction process, increasing the temperature of the bitumen extraction process, increasing the water addition rate to the bitumen extraction process, or increasing the caustic dosage or the other extraction chemical dosage to the bitumen extraction process. The process parameter may be a shoveling direction of the oil sand ore to move towards higher or lower quality ores.
[0036] Another use of this analysis may be in environmental fields as a tool to rapidly assess hydrocarbon contamination indirectly, expanding the use of XRF beyond metal content determination in hydrocarbon contaminated soils and sediments. XRF may also be used in high resolution geochemical logging of cores at the exploration stage, where the abundance of certain trace elements such as vanadium may serve as a proxy to organic enrichment, in addition to the properties described herein.
[0037] In the preceding description, for purposes of explanation, numerous details are set forth in order to provide a thorough understanding of the embodiments of the invention.
However, it will be apparent to one skilled in the art that these specific details are not required in order to practice the invention.
[0038] The above-described embodiments of the invention are intended to be examples only. Alterations, modifications and variations can be effected to the particular embodiments by those of skill in the art without departing from the scope of the invention, which is defined solely by the claims appended hereto.

Claims (8)

CLAIMS:
1. A method comprising:
a) measuring a sulfur content in a bitumen containing stream using X-Ray Fluorescence (XRF);
b) estimating a bitumen content in the bitumen containing stream based on the measured sulfur content;
c) comparing the sulfur content or the bitumen content to a predetermined reference range; and d) adjusting a process parameter, if necessary, based on the sulfur content or the bitumen content as compared to the predetermined reference range to adjust the bitumen content of the bitumen containing stream;
wherein the bitumen containing stream is boiler feed water in an in-situ bitumen recovery process, or oil sand ore.
2. The method of claim 1, wherein the bitumen containing stream is the boiler feed water in an in-situ bitumen recovery process.
3. The method of claim 2, wherein the process parameter is a flotation unit efficiency parameter, a hot lime softener efficiency parameter, a filter efficiency parameter, or a weak acid cation efficiency parameter.
4. The method of claim 3, wherein where the sulfur content or the bitumen content is above the predetermined reference range, at least one of the following actions are taken: increasing the flotation unit efficiency parameter, increasing the hot lime softener efficiency parameter, increasing the filter efficiency parameter, or increasing the weak acid cation efficiency parameter.
5. The method of claim 1, wherein the bitumen containing stream is the oil sand ore.
6. The method of claim 5, wherein the process parameter is an oil sand ore blending ratio to a bitumen extraction process, a temperature of the bitumen extraction process, a water addition rate to the bitumen extraction process, or a caustic dosage or other extraction chemical dosage to the bitumen extraction process.
7. The method of claim 6, wherein where the sulfur content or the bitumen content is above or below the predetermined reference range, at least one of the following actions are taken:
adjusting the oil sand ore blending ratio to the bitumen extraction process, increasing the temperature of the bitumen extraction process, increasing the water addition rate to the bitumen extraction process, or increasing the caustic dosage or the other extraction chemical dosage to the bitumen extraction process.
8. The method of claim 5, wherein the process parameter is a shoveling direction of the oil sand ore to move towards higher or lower quality ores.
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