CN102245505A - Process for treating a heavy hydrocarbon feedstock to reduce its viscosity - Google Patents
Process for treating a heavy hydrocarbon feedstock to reduce its viscosity Download PDFInfo
- Publication number
- CN102245505A CN102245505A CN2009801502271A CN200980150227A CN102245505A CN 102245505 A CN102245505 A CN 102245505A CN 2009801502271 A CN2009801502271 A CN 2009801502271A CN 200980150227 A CN200980150227 A CN 200980150227A CN 102245505 A CN102245505 A CN 102245505A
- Authority
- CN
- China
- Prior art keywords
- heavy hydrocarbon
- hydrocarbon feedstocks
- viscosity
- dithiocarbonic anhydride
- elemental sulfur
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
-
- 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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/02—Non-metals
Abstract
A process for reducing the viscosity a heavy hydrocarbon feedstock, comprising: supplying the heavy hydrocarbon feedstock and elemental sulphur to a reaction zone and reacting, in the liquid phase, at a temperature in the range of from 300 to 750 DEG C, a part of the heavy hydrocarbon feedstock with the elemental sulphur to form a reaction mixture comprising heavy hydrocarbon stream, carbon disulphide and hydrogen sulphide, followed by cooling the reaction mixture to provide treated heavy hydrocarbon stream comprising carbon disulphide. The invention also concerns products obtainable by the above process, as well as its use in pipeline transportation.
Description
Technical field
The invention provides and reduce the heavy hydrocarbon feedstocks method of viscosity, by the heavy hydrocarbon stream and the purposes of heavy hydrocarbon stream in pipe-line transportation of this method acquisition.
Background technology
Heavy hydrocarbon feedstocks, as heavy crude and pitch, particularly those that produce from some geo-logical terrain such as oil-sand may be relative tacks, promptly may have to make it be difficult to viscosity by pipe-line transportation.The sticky property of heavy hydrocarbon feed is called " low-gravity " oil in petroleum industry; Height ratio heavy oil is the oil of sparse relatively and relatively easy pumping.
By US 5025863, US 5104516 and FR2484603 become known for reducing the several methods and the system of heavy hydrocarbon feedstocks viscosity.
Disclose a kind of method among the US 6644334, described method is passed through under high pressure crude oil to be injected in the combination of gas or gas, thereby reduces the viscosity of crude oil.Especially, described method relates to carbonic acid gas (CO
2) or CO more preferably
2Inject crude oil with the combination of nitrogen.The shortcoming of this method is by the viscosity that crude oil reduces crude oil is injected in the combination of gas or gas, must carry out under high gaseous tension.
Dithiocarbonic anhydride is known to be the suitable solvent that is used for enhanced oil recovery.For example among the US 3847221, disclose and utilized dithiocarbonic anhydride to gather from the heavy hydrocarbon feedstocks of oil-sand to strengthen by miscible displacement.The key (slug) that this method relates to the solvent mixture of the heavy hydrocarbon feedstocks that will be used for gathering from oil-sand injects reservoir, and the density of this solvent is equal to or greater than water and comprises dithiocarbonic anhydride and aromatic hydrocarbon or aliphatic hydrocarbon.After solvent mixture, aqueous fluid is introduced in the reservoir, pass through reservoir to order about solvent.Heavy hydrocarbon feedstocks and solvent move towards the position that is lower than solvent introducing position, there the output heavy hydrocarbon stream.
The shortcoming of above-mentioned art methods is that described method requires to introduce the fresh solvent in the reservoir.This method effectively plays a role for reducing heavy hydrocarbon feedstocks viscosity, makes more effectively pumping heavy hydrocarbon feedstocks, but is expensive and is unpractical in many application.
Summary of the invention
Have been found that and under the condition of not adding any fresh solvent or solvent mixture, can reduce the viscosity of heavy hydrocarbon feedstocks.By elemental sulfur being added heavy hydrocarbon and under 300-750 ℃ temperature, heats, the viscosity of reduction heavy hydrocarbon feedstocks that can be favourable.This will cause heavy hydrocarbon feedstocks and elemental sulfur partly to change into dithiocarbonic anhydride and hydrogen sulfide.Reaction mixture will produce dithiocarbonic anhydride wherein and be dissolved in product in the heavy hydrocarbon feedstocks.
Therefore, the invention provides and be used to reduce the heavy hydrocarbon feedstocks method of viscosity, comprising:
Heavy hydrocarbon feedstocks and elemental sulfur are supplied to reaction zone, under 300-750 ℃ temperature, a part heavy hydrocarbon feedstocks and elemental sulfur react the reaction mixture that formation comprises heavy hydrocarbon stream, dithiocarbonic anhydride and hydrogen sulfide in liquid phase, reaction mixture is to provide heavy hydrocarbon stream after the processing that comprises dithiocarbonic anhydride subsequently.
The advantage of described method is under the condition of not adding fresh solvent or solvent mixture, and the viscosity of heavy hydrocarbon feedstocks reduces.By this way, the cost of the inventive method fully reduces.In addition, original position reduces the viscosity of heavy hydrocarbon feedstocks.
The present invention also provides can be by the product of described method acquisition.The viscosity of the product that forms by described method is generally 50-10000mPa/s, preferred 100-1000mPa/s.By this way, improved the flowability of heavy hydrocarbon stream.
The invention still further relates to the purposes of product in pipe-line transportation that described method obtains.
The advantage of the purposes of product in pipe-line transportation that can obtain by described method is the Canadian pipeline specifications that the product that makes can satisfy the viscosity of 250cSt (250mPa/s).
In the methods of the invention, under 300-750 ℃ temperature, heavy hydrocarbon feedstocks reacts mutually with elemental sulfur.
Elemental sulfur can be introduced with the form of vapor phase or liquid phase.Preferably, elemental sulfur is a liquid elemental sulfur phase.Liquid sulfur can comprise S mutually
2, S
8, S
∞Or the sulphur of their form of mixtures.Usually, the fusing point of sulphur is 96-116 ℃.Liquid sulfur phase and heavy hydrocarbon feedstocks are added reaction zone, wherein their interreactions in liquid phase.Reaction zone is reactor vessel or pipe typically.Heavy hydrocarbon feedstocks can be supplied to the reaction zone that comprises liquid elemental sulfur phase.
Heavy hydrocarbon feedstocks can be a derive pitch or be at least 99.5% slag oil asphalt by distillation, the particularly underpressure distillation of heavy crude or the oil-sand long residuum, the particularly solubleness in dithiocarbonic anhydride that the bituminous underpressure distillation obtains of deriving of oil-sand.
Heavy hydrocarbon feedstocks comprises hydrocarbon compound, and described hydrocarbon compound has carbon and hydrogen atom and optional heteroatoms in a small amount for example oxygen, sulphur or nitrogen.Hydrocarbon compound is a liquid under the reaction conditions of using.The initial boiling point of heavy hydrocarbon feedstocks can be 350-850 ℃.
In the methods of the invention, hydrocarbon compound and elemental sulfur interreaction.The W-response equation is:
C
x?H
y+(2x+1/2y)S→xCS
2+1/2yH
2S
Heavy hydrocarbon feedstocks can comprise greater than a kind of hydrocarbon compound.
In the methods of the invention, heavy hydrocarbon feedstocks and elemental sulfur all will be continuously supplied to reaction zone usually.Compatibly, by making heavy hydrocarbon feedstocks and liquid sulfur pre-mixing mutually, heavy hydrocarbon feedstocks is supplied to reaction zone.The simple substance sulfur content that adds reaction zone is 1-25wt%, based on heavy hydrocarbon stream.
Preferred 1-3600 second duration of contact of heavy hydrocarbon feedstocks and liquid sulfur, preferred 5-600 second.
In the methods of the invention, the liquid elemental sulfur remains under 250-750 ℃ the temperature mutually.Be lower than under 250 ℃ the temperature, the high viscosity of liquid sulfur phase will hinder suitable processing.Preferably, temperature is 350-700 ℃, more preferably 400-650 ℃.
Reactant reacts being enough to keep under the pressure of liquid elemental sulfur phase mutually.Therefore, pressure can depend on temperature of reaction strongly.Preferably, the pressure in the reaction zone is 3-200bar (definitely), more preferably 4-100bar (definitely), even more preferably 5-30bar (definitely).
In the methods of the invention, form the reaction mixture that comprises heavy hydrocarbon stream, dithiocarbonic anhydride and hydrogen sulfide.This reaction mixture is delivered to second reactor vessel or pipe, thereby wherein reaction mixture obtains to comprise the liquid stream of dithiocarbonic anhydride.
The preferred 1-25wt% of dithiocarbonic anhydride amount that forms is based on the weight of heavy hydrocarbon.Usually, the liquid stream that comprises dithiocarbonic anhydride that obtains by the inventive method also comprises hydrogen sulfide.
Typical concentration of hydrogen sulfide is the hydrogen sulfide of 0.05-50wt%, particularly 0.2-10wt%, based on the amount of heavy hydrocarbon.
After reaction was finished, cooling mixture caused heavy hydrocarbon viscosity to reduce.The product that comprises heavy hydrocarbon, dithiocarbonic anhydride and hydrogen sulfide that part transforms has 50-10000mPa/s, the more preferably viscosity of the reduction of 100-1000mPa/s.
Reaction between known heavy hydrocarbon and the sulphur can be carried out in the presence of catalyzer, for example described in EP06116866.2.Preferably, hydrocarbon compound and sulphur react under the condition that does not have catalyzer.
Preferably, the inventive method comprises heavy hydrocarbon feedstocks is divided into two raw materials (first and second raw materials), and first raw material and elemental sulfur react in reaction zone and will handle back first logistics and second material combination in second container or pipe thus.Preferably, first raw material is 1-50wt%, particularly 5-40wt%, based on heavy hydrocarbon feedstocks weight.By this way, only need the heavy hydrocarbon feedstocks of 1-50wt% is heated to 300-750 ℃ temperature, with the product of the present invention of the viscosity that obtains to have identical reduction as mentioned above.
The product that comprises dithiocarbonic anhydride of Xing Chenging is particularly suitable for carrying by pipeline in the methods of the invention, because it for example will satisfy the requirement for the Canadian specification of pipe-line transportation usually.
The product that comprises dithiocarbonic anhydride can be carried being generally under 5-80 ℃ the temperature.The heating of pipeline not necessarily.Therefore, can reduce by 30-80 ℃, preferred 40-60 ℃ temperature, and reduce delivery temperature.By this way, the conveying of heavy hydrocarbon feedstocks is economically feasible.
Compatibly, can from reaction mixture, remove hydrogen sulfide by the gas/liquid separation.Randomly,, can pass through gas stream for example nitrogen, carbonic acid gas or methane stripping liquid stream, reaction mixture is further purified removal hydrogen sulfide at the gas/liquid after separating.
Compatibly, after pipe-line transportation, can from reaction mixture, remove hydrogen sulfide.Randomly, isolating hydrogen sulfide can be changed into elemental sulfur, for example in the Claus method and be circulated to reaction zone.The hydrogen sulfide amount of removing from reaction mixture is the hydrogen sulfide of 0.05-40wt%, particularly 0.2-10wt%, based on the amount of heavy hydrocarbon.
After pipe-line transportation, can from heavy hydrocarbon stream, separate dithiocarbonic anhydride.The separation of dithiocarbonic anhydride can be undertaken by any suitable method, for example distillation.Isolating dithiocarbonic anhydride preferred cycle and mix at mixing vessel or Guan Zhongyu heavy hydrocarbon.
Because the formation of dithiocarbonic anhydride, the viscosity of heavy hydrocarbon stream can reduce 10-99.9%, particularly 80-99%, represents with mPa/s.
Further describe the inventive method by following non-limiting examples.
Embodiment
The long boiling range residual oil of Peace River pitch (PR-B) and Peace River (PR-LR) has full-bodied mink cell focus.Use dithiocarbonic anhydride to reduce by two kinds of oil viscosities.Tested the mixture of several oil and dithiocarbonic anhydride, to measure of the influence of dithiocarbonic anhydride/oil ratio to viscosity.
Embodiment 1
In vial, a certain amount of dithiocarbonic anhydride added 31.1 gram PR-LR (44.9mmol), with preparation based on 1.2,5,10,15 and the PR-LR sample of the dithiocarbonic anhydride of 40wt%.After interpolation finishes, shook mixture 1 hour, so that dithiocarbonic anhydride dissolving and obtain uniform liquid.HAAKE viscosity tester Typle 7R plus (Thermo Electron, GmbH) on, the viscosity of measure sample in the controlled temperature bath under several temperature.Table 1 has shown the viscosity data of PR-LR.The %wt of dithiocarbonic anhydride in oil that calculates is based on the total amount of oil and dithiocarbonic anhydride.
The result of table 1 shows that by adding dithiocarbonic anhydride, the viscosity of PR-LR reduces.The amount that increases dithiocarbonic anhydride has further reduced viscosity.In addition, under differing temps, when using similar PR-LR weight ratio, viscosity raises along with temperature and reduces.This observations shows, dissolving and the viscosity temperature sensitivity of dithiocarbonic anhydride in oil.
Embodiment 2
In vial, a certain amount of dithiocarbonic anhydride added 31.1 gram PR-B (46.8mmol), with preparation based on 0,1.2,6.2,10.5 and the PR-LR sample of the dithiocarbonic anhydride of 20.1wt%.As among the embodiment 1, carry out identical program.Table 2 has shown the result of PR-B.The %wt of dithiocarbonic anhydride in oil that calculates is based on the total amount of oil and dithiocarbonic anhydride.
Result in the table 2 shows, compares with the result who utilizes PR-B to obtain, and uses dithiocarbonic anhydride to obtain similar result in PR-R.
Table 1
Table 2
Claims (12)
1. be used to reduce the heavy hydrocarbon feedstocks method of viscosity, comprise:
Heavy hydrocarbon feedstocks and elemental sulfur are supplied to reaction zone, under 300-750 ℃ temperature, a part heavy hydrocarbon feedstocks and elemental sulfur react the reaction mixture that formation comprises heavy hydrocarbon stream, dithiocarbonic anhydride and hydrogen sulfide in liquid phase, reaction mixture is to provide heavy hydrocarbon stream after the processing that comprises dithiocarbonic anhydride subsequently.
2. the process of claim 1 wherein that the simple substance sulfur content that adds reaction zone is 1-25wt%, based on heavy hydrocarbon stream.
3. claim 1 or 2 method, wherein the dithiocarbonic anhydride amount of Xing Chenging is 2-25wt%, based on heavy hydrocarbon feedstocks weight, preferred 5-20wt%.
4. each method of claim 1-3, wherein heavy hydrocarbon feedstocks is a heavy crude, preferred residue mink cell focus.
5. each method of claim 1-4, wherein heavy hydrocarbon feedstocks is a pitch.
6. each method of claim 1-5 is wherein separated, is utilized gas stream stripping liquid stream after optional by gas/liquid, removes the hydrogen sulfide that forms from reaction mixture.
7. each method of claim 1-6, wherein elemental sulfur is a liquid elemental sulfur phase.
8. each method of claim 1-7 wherein is divided into heavy hydrocarbon feedstocks two raw materials, first raw material and elemental sulfur reaction and will handle the logistics afterwards and second material combination.
9. each method of claim 1-8, wherein the pressure in the reaction zone is 3-200bara (definitely), more preferably 5-30bara (definitely).
10. the product that can obtain by each method of claim 1-9, the viscosity of preferred wherein said product is 50-10000mPa/s, more preferably 100-1000mPa/s.
11. the purposes of the product of claim 10 in pipe-line transportation.
12. the product purposes of claim 11 is at 5-80.℃ temperature under.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP08171615.1 | 2008-12-15 | ||
| EP08171615 | 2008-12-15 | ||
| PCT/EP2009/067046 WO2010069907A1 (en) | 2008-12-15 | 2009-12-14 | Process for treating a heavy hydrocarbon feedstock to reduce its viscosity |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102245505A true CN102245505A (en) | 2011-11-16 |
Family
ID=40602409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009801502271A Pending CN102245505A (en) | 2008-12-15 | 2009-12-14 | Process for treating a heavy hydrocarbon feedstock to reduce its viscosity |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20110259791A1 (en) |
| CN (1) | CN102245505A (en) |
| CA (1) | CA2746842A1 (en) |
| EA (1) | EA201100957A1 (en) |
| WO (1) | WO2010069907A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105883808A (en) * | 2014-11-07 | 2016-08-24 | 王兴路 | Method for preparing carbon disulfide |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB201200155D0 (en) * | 2012-01-06 | 2012-02-15 | Statoil Asa | Process |
| US10851314B2 (en) | 2019-04-17 | 2020-12-01 | Saudi Arabian Oil Company | Method to improve the efficiency of pipeline transportation of heavy oils |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1981161A (en) * | 1931-12-11 | 1934-11-20 | Meigs Bassett & Slaughter Inc | Preparation of carbon disulphide and hydrogen sulphide |
| US2492719A (en) * | 1943-06-26 | 1949-12-27 | Pure Oil Co | Preparation of carbon disulfide |
| US2556177A (en) * | 1948-08-17 | 1951-06-12 | Great Lakes Carbon Corp | Process for production of carbon disulfide |
| US3087788A (en) * | 1959-04-06 | 1963-04-30 | Fmc Corp | Combined catalytic and non-catalytic process of producing hydrogen sulfide and carbon disulfide |
| FR1493586A (en) * | 1966-06-15 | 1967-09-01 | Progil | Carbon disulphide manufacturing process |
| CN101166889B (en) * | 2005-04-21 | 2012-11-28 | 国际壳牌研究有限公司 | Systems and methods for producing oil and/or gas |
| EA014708B1 (en) * | 2006-05-16 | 2011-02-28 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. | A process for the manufacture of carbon disulphide |
| EA014709B1 (en) * | 2006-05-16 | 2011-02-28 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. | A process for the manufacture of carbon disulphide |
| CN101489930A (en) * | 2006-07-07 | 2009-07-22 | 国际壳牌研究有限公司 | Process for the manufacture of carbon disulphide and use of a liquid stream comprising carbon disulphide for enhanced oil recovery |
| CA2660296C (en) * | 2006-08-10 | 2015-10-13 | Shell Internationale Research Maatschappij B.V. | Methods for producing oil and/or gas |
-
2009
- 2009-12-14 WO PCT/EP2009/067046 patent/WO2010069907A1/en active Application Filing
- 2009-12-14 EA EA201100957A patent/EA201100957A1/en unknown
- 2009-12-14 CN CN2009801502271A patent/CN102245505A/en active Pending
- 2009-12-14 US US13/139,403 patent/US20110259791A1/en not_active Abandoned
- 2009-12-14 CA CA2746842A patent/CA2746842A1/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105883808A (en) * | 2014-11-07 | 2016-08-24 | 王兴路 | Method for preparing carbon disulfide |
Also Published As
| Publication number | Publication date |
|---|---|
| US20110259791A1 (en) | 2011-10-27 |
| WO2010069907A1 (en) | 2010-06-24 |
| CA2746842A1 (en) | 2010-06-24 |
| EA201100957A1 (en) | 2011-12-30 |
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Application publication date: 20111116 |