CA2428995A1 - Separation of asphaltenes from bitumen and heavy oils using a metal salt catalyst - Google Patents
Separation of asphaltenes from bitumen and heavy oils using a metal salt catalyst Download PDFInfo
- Publication number
- CA2428995A1 CA2428995A1 CA002428995A CA2428995A CA2428995A1 CA 2428995 A1 CA2428995 A1 CA 2428995A1 CA 002428995 A CA002428995 A CA 002428995A CA 2428995 A CA2428995 A CA 2428995A CA 2428995 A1 CA2428995 A1 CA 2428995A1
- Authority
- CA
- Canada
- Prior art keywords
- asphaltenes
- separation
- limited
- bitumen
- oil sands
- 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.)
- Abandoned
Links
Classifications
-
- 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
- C10G29/06—Metal salts, or metal salts deposited on a carrier
- C10G29/12—Halides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/0208—Separation of non-miscible liquids by sedimentation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/0217—Separation of non-miscible liquids by centrifugal force
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/04—Breaking emulsions
- B01D17/047—Breaking emulsions with separation aids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
In the present invention a method for the separation of asphaltenes from, beat not limited to, oil sands bitumen, water slurry based oil sands extraction froth, heavy oils and heavy fractions of the refinery products by using the catalytic effect of metal salts, such as, belt not limited to aluminum chloride (AlCl3), zinc chloride (ZnCl2) and ferric chloride (FeCl3) as catalyst to promote intra molecular condensation between the asphaltene molecules similar to the Friedel-Crafts type alkylation reactions to condensate and flocculate asphaltenes for their rapid separation and precipitation. The precipitated asphaltenes are easily separated by density difference using gravitational or centrifuge settling apparatus. Separation of asphaltenes using the present invention could be applied to, but not limited to, asphaltene containing hydrocarbon fluid mixtures, oil sands bitumen, heavy oils and hydrocarbon-water emulsion systems containing solids such as sands, silt and clays.
Description
Sepa:~atiodd ofAsp6dallenes frodn Bltl11926rr urru rrwr.-y vrre uorrrg a1 /~BfQr."lldjt ~"atldlJ~St l'13~e ~~'S~r~Ip~l01'H
Eacliaround of the Invention The fraction of petroleum (crude oil, heavy oil or bitumen) which is insoluble in rz-pentane or n-heptane and soluble in benzene is defined as asphaltenes.
Asphaltencs ar;, the highest molecular weight fraction of the oil sands bitumen, with an average molecular weight of about 3,600. The average molecular weight of the asphaltenes could lye different for different hydrocarbons.
Athabasca oil sands bitumen of Alberta, Canada contains about 14 % to 22 ~ o asphaltenes. Athabasca oil sands asphaltenes are composed' of about 79.9 °~o carbon (C), 8.3 % hydrogen (H), 1.2 % nitrogen (N), 7.6 % sulfur {S), 3.2 % oxygen (O), which corresponds to atomic H/C ratio of 1.24. Asphaltene molecules are known as coke precursors, because of their tendency to produce poke by thermal cracking reaction upon heating.
Presence of asphaltenes molecules, as an example, in oil sands bitumen creates problems during the pipe-line transportation of bitumen. In pipe-line transportation.
addition o I' light hydrocarbons is generally used to reduce the viscosity of bitumen.
Separation and precipitation of asphaltenes in the bitumen light hydrocarbon mixture in the pipe-l.i.n;.
causes plugging problems. A mild thermal or catalytic cracking, which i.s also called visbreaking, as an example, may be used to reduce oil sands bitumen viscosit~r Asphaltenes present in mildly cracked bitumen may also create problems during the pipe-line transportation because of the separation and the precipitation of asphaltenes in tile:
pipe-line.
Presence of asphaltenes, as an example, in bitumen also creates problems during the upgrading of bitumen to synthetic crude oil, because of the tendency of asphaltenes t<>
produce coke and to poison the active sites of the hydrotreating and/or hydrocrackir~:~
catalysts. As a result, a primary upgrading process, also called coking, is generally used to eliminate the asphaltenes. Using the coking process, as an example, bitumen is converted into petroleum coke, coker gas oil and light hydrocarbon gases by thf:rm cracking reactions.
Separation of asphaltenes, as an example, from oil sands bitumen, heavy oils or heavy end of the refinery products is applied in the oil industry. Separation of asphaltenes is Separation ofAsphaltenes from Bitumen and Heavy Oils using a Metal Salt Catalyst i'ccge s generally achieved by diluting the asphaltene containing hydrocarbons by ligL,t hydrocarbons, such as pentene or hexane. Because of the solubility limitations, i:lv asphaltenes are separated from the solution. Centrifuge is a commonly used practice tv-precipitate already separated asphaltenes.
The Present Invention In the present invention separation of asphaltenes is enhanced by increasing tr,a molecular weight of the asphaltenes by intra molecular condensation and flocculation cwf the asphaltene molecules using the Friedel-Crafts type alkylation reactions.
Thes;.
reactions are promoted by the catalytic effect of metal salts, such as but not limit;,d ia:
aluminum chloride (AlCl3), zinc chloride (ZnCl2) and ferric chloride (FeC'l3).
~(Jsing th:::
the Friedel-Crafts type alkylation reactions, asphaltene molecules are combined together between the aromatic and aliphatic functional groups as depicted, but not limited to b5,~
tl~e following chemical reaction:
<4sphaltenel - C6 H5 + Asphaltene2 - R - A~ Asphaltene, - C6 H4 - R -.4.~phw'te~ez where, Asphaltenel and Asphaltene2 are the two different asphlatene molecules containing aromatic (C6H5) and aliphatic (R) functional groups, respectively.
This reaction is catalyzed by the metal salts such as aluminum chloride (AlCl3), zinc chloriC?c (ZnCl2) and ferric chloride (FeCl3).
The extents of the Friedel-Crafts type alkylation reactions would be controlled by trAe reactor operating conditions, composition of the reacting system, catalyst, «~ater, dilueoT;t hydrocarbons, solids and concentration of the asphaltenes, temperature, an~~bility of tr s asphaltenes, mixing, etc. As the extents of the Friedel-Crafts type alkylation reactions increase by eliminating the rate controlling steps and providing the sufficient operatin?
conditions, the magnitude of the intra molecular condensation and flc~ccul~tior:: c:1' asphaltenes also increases, which results in a sharp reduction in the solubi.li'.y c~f asphaltenes, and eventually the separation and the precipitation of the aspha.ltenes.
Effects of different metal salts on the separation of asphaltenes are presented in .~ i.g~re and Figure 4. Effect of the metal salts on the separation of asphaltenes would be ~:
function of the nature of the asphaltenes containing mixture.
The present invention could find applications in the separation of aspl?.altenes fror:-~.
asphaltenes containing mixtures, such as but not limited to oil sands bitumen and water slurry based oil sands extraction froth.
Smnr~nary of the Invention A primary objective of the present invention is to provide an improved process or rnetho_i for the separation of asphaltenes. The present invention is based on the intra malecul condensation between the asphaltene molecules similar to the Friedel-Crafts type;
alkylation reactions to condensate and flocculate a.sphaltenes for their rapid separatio-~-~
. . . .. ..W..: r . ", ... . ,.,. , . -.,: . . . .. ~w . ..
Separation of Asphaltenes from Bitumen and Heavy Oils using a Metal Salt Catalyst .t'c~ge and precipitation. The present invention uses the catalytic effect of metal salts, su~;,i~ u,~
but not limited to aluminum chloride (AlCl3), zinc chloride (ZnCl2) and ferric chloric~", (FeCl3) to promote the Friedel-Crafts type alkylation reactions.
The present invention could be applied commercially for the separation of aspl~alter;e from asphaltenes containing hydrocarbon mixtures, including the mixtures containir.~=
water and solids, such as sand, silt and clay.
ether prior art considers thickening apparatus of interest hereto includes ~J.~, f'at. I~(o;s.
4,846,957; 4,124,486; 4,865,741; 4,155,833 and Canadian Pat. No:>.
1,330,06.'?;
1,192,520; 2,063,101; 1,177,770; 1,100,080; 1,256,392; 1.207.,699; 1,:~90,i71;
Eacliaround of the Invention The fraction of petroleum (crude oil, heavy oil or bitumen) which is insoluble in rz-pentane or n-heptane and soluble in benzene is defined as asphaltenes.
Asphaltencs ar;, the highest molecular weight fraction of the oil sands bitumen, with an average molecular weight of about 3,600. The average molecular weight of the asphaltenes could lye different for different hydrocarbons.
Athabasca oil sands bitumen of Alberta, Canada contains about 14 % to 22 ~ o asphaltenes. Athabasca oil sands asphaltenes are composed' of about 79.9 °~o carbon (C), 8.3 % hydrogen (H), 1.2 % nitrogen (N), 7.6 % sulfur {S), 3.2 % oxygen (O), which corresponds to atomic H/C ratio of 1.24. Asphaltene molecules are known as coke precursors, because of their tendency to produce poke by thermal cracking reaction upon heating.
Presence of asphaltenes molecules, as an example, in oil sands bitumen creates problems during the pipe-line transportation of bitumen. In pipe-line transportation.
addition o I' light hydrocarbons is generally used to reduce the viscosity of bitumen.
Separation and precipitation of asphaltenes in the bitumen light hydrocarbon mixture in the pipe-l.i.n;.
causes plugging problems. A mild thermal or catalytic cracking, which i.s also called visbreaking, as an example, may be used to reduce oil sands bitumen viscosit~r Asphaltenes present in mildly cracked bitumen may also create problems during the pipe-line transportation because of the separation and the precipitation of asphaltenes in tile:
pipe-line.
Presence of asphaltenes, as an example, in bitumen also creates problems during the upgrading of bitumen to synthetic crude oil, because of the tendency of asphaltenes t<>
produce coke and to poison the active sites of the hydrotreating and/or hydrocrackir~:~
catalysts. As a result, a primary upgrading process, also called coking, is generally used to eliminate the asphaltenes. Using the coking process, as an example, bitumen is converted into petroleum coke, coker gas oil and light hydrocarbon gases by thf:rm cracking reactions.
Separation of asphaltenes, as an example, from oil sands bitumen, heavy oils or heavy end of the refinery products is applied in the oil industry. Separation of asphaltenes is Separation ofAsphaltenes from Bitumen and Heavy Oils using a Metal Salt Catalyst i'ccge s generally achieved by diluting the asphaltene containing hydrocarbons by ligL,t hydrocarbons, such as pentene or hexane. Because of the solubility limitations, i:lv asphaltenes are separated from the solution. Centrifuge is a commonly used practice tv-precipitate already separated asphaltenes.
The Present Invention In the present invention separation of asphaltenes is enhanced by increasing tr,a molecular weight of the asphaltenes by intra molecular condensation and flocculation cwf the asphaltene molecules using the Friedel-Crafts type alkylation reactions.
Thes;.
reactions are promoted by the catalytic effect of metal salts, such as but not limit;,d ia:
aluminum chloride (AlCl3), zinc chloride (ZnCl2) and ferric chloride (FeC'l3).
~(Jsing th:::
the Friedel-Crafts type alkylation reactions, asphaltene molecules are combined together between the aromatic and aliphatic functional groups as depicted, but not limited to b5,~
tl~e following chemical reaction:
<4sphaltenel - C6 H5 + Asphaltene2 - R - A~ Asphaltene, - C6 H4 - R -.4.~phw'te~ez where, Asphaltenel and Asphaltene2 are the two different asphlatene molecules containing aromatic (C6H5) and aliphatic (R) functional groups, respectively.
This reaction is catalyzed by the metal salts such as aluminum chloride (AlCl3), zinc chloriC?c (ZnCl2) and ferric chloride (FeCl3).
The extents of the Friedel-Crafts type alkylation reactions would be controlled by trAe reactor operating conditions, composition of the reacting system, catalyst, «~ater, dilueoT;t hydrocarbons, solids and concentration of the asphaltenes, temperature, an~~bility of tr s asphaltenes, mixing, etc. As the extents of the Friedel-Crafts type alkylation reactions increase by eliminating the rate controlling steps and providing the sufficient operatin?
conditions, the magnitude of the intra molecular condensation and flc~ccul~tior:: c:1' asphaltenes also increases, which results in a sharp reduction in the solubi.li'.y c~f asphaltenes, and eventually the separation and the precipitation of the aspha.ltenes.
Effects of different metal salts on the separation of asphaltenes are presented in .~ i.g~re and Figure 4. Effect of the metal salts on the separation of asphaltenes would be ~:
function of the nature of the asphaltenes containing mixture.
The present invention could find applications in the separation of aspl?.altenes fror:-~.
asphaltenes containing mixtures, such as but not limited to oil sands bitumen and water slurry based oil sands extraction froth.
Smnr~nary of the Invention A primary objective of the present invention is to provide an improved process or rnetho_i for the separation of asphaltenes. The present invention is based on the intra malecul condensation between the asphaltene molecules similar to the Friedel-Crafts type;
alkylation reactions to condensate and flocculate a.sphaltenes for their rapid separatio-~-~
. . . .. ..W..: r . ", ... . ,.,. , . -.,: . . . .. ~w . ..
Separation of Asphaltenes from Bitumen and Heavy Oils using a Metal Salt Catalyst .t'c~ge and precipitation. The present invention uses the catalytic effect of metal salts, su~;,i~ u,~
but not limited to aluminum chloride (AlCl3), zinc chloride (ZnCl2) and ferric chloric~", (FeCl3) to promote the Friedel-Crafts type alkylation reactions.
The present invention could be applied commercially for the separation of aspl~alter;e from asphaltenes containing hydrocarbon mixtures, including the mixtures containir.~=
water and solids, such as sand, silt and clay.
ether prior art considers thickening apparatus of interest hereto includes ~J.~, f'at. I~(o;s.
4,846,957; 4,124,486; 4,865,741; 4,155,833 and Canadian Pat. No:>.
1,330,06.'?;
1,192,520; 2,063,101; 1,177,770; 1,100,080; 1,256,392; 1.207.,699; 1,:~90,i71;
2,277,052;
Claims (2)
- Claim 1. A process as depicted in Figure 1 for the separation of asphaltenes from asphaltene containing hydrocarbon fluid mixtures, such as, hut not limited to:
oil sands bitumen, heavy oils and heavy fractions of the refinery products. - Claim 2. A process as depicted in Figure 2 for the separation of asphaltenes from asphaltenes containing hydrocarbon-water emulsion systems probably also containing solids such as sands, silt and clays, such as but not limited to water slurry based oil sands extraction froth.
Claim 1 and Claim 2 comprise:
a. using metal salts, such as, but not limited to aluminum chloride (AlCl3), zinc chloride (ZnCl2) and ferric chloride (FeCl3) as catalyst for the Friedel-Crafts type alkylation reactions to condensate asphaltenes for their rapid flocculation, precipitated and separation.
b. using continuous, batch or semi-batch reactor or reactors, preferably operating at atmospheric pressure, to provide the sufficient residence time to achieve the desired extents for the Friedel-Crafts type alkylation reactions.
c. using condensers attached the reactor or reactors, preferably to operate the reactor or reactors at atmospheric pressures and at desired temperatures, at which a fraction of the reactor content may be in the gaseous phase.
d. using a process by adding proper amount of water and light hydrocarbons, if necessary, into the asphaltene containing mixture, to increase the asphaltene mobility and catalysts effectiveness.
e. using a method to precipitate the condensed and flocculated asphaltenes, such as using the gravity separation, the centrifuge separation or both, for final separation and precipitation of the condensed and flocculated asphaltenes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002428995A CA2428995A1 (en) | 2003-05-16 | 2003-05-16 | Separation of asphaltenes from bitumen and heavy oils using a metal salt catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002428995A CA2428995A1 (en) | 2003-05-16 | 2003-05-16 | Separation of asphaltenes from bitumen and heavy oils using a metal salt catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2428995A1 true CA2428995A1 (en) | 2004-11-16 |
Family
ID=33437996
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002428995A Abandoned CA2428995A1 (en) | 2003-05-16 | 2003-05-16 | Separation of asphaltenes from bitumen and heavy oils using a metal salt catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2428995A1 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011006312A1 (en) * | 2009-07-15 | 2011-01-20 | Niu Bin | Process for pruifying oil products |
| WO2012013142A1 (en) * | 2010-07-27 | 2012-02-02 | 中国石油大学(华东) | Heavy oil processing |
| CN103173235A (en) * | 2013-03-27 | 2013-06-26 | 天津大学 | Low-energy-consumption removal method of quinoline insolubles in asphalt |
| US8529687B2 (en) * | 2006-06-08 | 2013-09-10 | Marathon Oil Canada Corporation | Oxidation of asphaltenes |
| CN114479896A (en) * | 2020-10-26 | 2022-05-13 | 中国石油天然气股份有限公司 | Method for separating petroleum asphalt component |
| CN114621598A (en) * | 2022-04-25 | 2022-06-14 | 西南交通大学 | Stable asphalt with high oil sand asphaltene mixing amount and preparation method thereof |
| US11377560B2 (en) | 2018-12-18 | 2022-07-05 | ExxonMobil Technology and Engineering Company | Modified asphalts and methods for producing the same |
-
2003
- 2003-05-16 CA CA002428995A patent/CA2428995A1/en not_active Abandoned
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8529687B2 (en) * | 2006-06-08 | 2013-09-10 | Marathon Oil Canada Corporation | Oxidation of asphaltenes |
| WO2011006312A1 (en) * | 2009-07-15 | 2011-01-20 | Niu Bin | Process for pruifying oil products |
| WO2012013142A1 (en) * | 2010-07-27 | 2012-02-02 | 中国石油大学(华东) | Heavy oil processing |
| CN103173235A (en) * | 2013-03-27 | 2013-06-26 | 天津大学 | Low-energy-consumption removal method of quinoline insolubles in asphalt |
| US11377560B2 (en) | 2018-12-18 | 2022-07-05 | ExxonMobil Technology and Engineering Company | Modified asphalts and methods for producing the same |
| CN114479896A (en) * | 2020-10-26 | 2022-05-13 | 中国石油天然气股份有限公司 | Method for separating petroleum asphalt component |
| CN114479896B (en) * | 2020-10-26 | 2023-04-25 | 中国石油天然气股份有限公司 | Method for separating petroleum asphalt component |
| CN114621598A (en) * | 2022-04-25 | 2022-06-14 | 西南交通大学 | Stable asphalt with high oil sand asphaltene mixing amount and preparation method thereof |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |