CN100391601C - Catalyst for downhole catalytic reforming of viscous crude - Google Patents
Catalyst for downhole catalytic reforming of viscous crude Download PDFInfo
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- CN100391601C CN100391601C CNB2006100264715A CN200610026471A CN100391601C CN 100391601 C CN100391601 C CN 100391601C CN B2006100264715 A CNB2006100264715 A CN B2006100264715A CN 200610026471 A CN200610026471 A CN 200610026471A CN 100391601 C CN100391601 C CN 100391601C
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Abstract
The present invention discloses a catalyst for the downhole catalytic reforming of viscous crude, which is colloid solution of transition metal; the solute of the present invention is colloid particles of hydrous oxide of transition metal, and the solvent is water, organic solvent or both mixture. When in use, under the precondition of not changing the thermal recovery process, an injection mode of a preflush slug is adopted; the solution concentration of the catalyst is 0.001% to 2.0 wt%, and the catalyst consumption is 3.0 wt% of the processing oil mass. The present invention has a certain catalytic effect to the thick oil. After reaction is carried out, the content of asphaltenes of heavy components in the thick oil descends; the viscosity is reduced, and the thick oil is partially lightened.
Description
Technical field
The present invention relates to catalyst technical field, specifically a kind of catalyst that is used for downhole catalytic reforming of viscous crude.
Background technology
As far back as 1986, Canadian scholar Hyne and partner thereof just found, simulate under the steam injection condition, and oil sands bitumen generation chemical change, heavy ends content reduces in the pitch, and lighter hydrocarbons content increases, and is referred to as the hydrothermal cracking reaction.Discovering afterwards, under simulation steam injection condition, after the certain density transition metal salt solution of adding, viscosity of thickened oil declines to a great extent in viscous crude, and asphalt content obviously reduces, and saturated hydrocarbon content increases, and gas yield rises.As seen transition metal ions reacts hydrothermal cracking and has played catalytic action.
American scholar McFarlane etc. have introduced a kind of oil-soluble catalyst ammonium heptamolybdate in its patent (USP5916432), can be used for the ground upgrading of heavy crude.Also have American scholar Clough in its patent (USP4846274), to report, adopt to contain V, Fe, the aqueous solution of transition metal ions such as Mn, catalytic reforming heavy crude under the steam soak temperature.Chinese Fan Hong richness is in its article (" slaine is to Liaohe River thick oil hydrothermal cracking reaction influence research " chemistry of fuel journal, October calendar year 2001,29; 5) talk about under the simulation steam injection condition, eight kinds of transition metal saline solutions such as iron, cobalt and nickel obtain good result to the catalytic performance of Liaohe River viscous crude.
Domestic scholars imagination is at the downhole catalytic reforming viscous crude, mainly is by adding suitable catalyst and auxiliary agent to oil reservoir, deepens the degree of the hydrothermal cracking reaction that viscous crude takes place under EOR Conditions, irreversibly reduces viscosity of thickened oil.This just makes the viscous crude lighting to a certain extent, has reduced thickened oil recovery, has collected defeated and difficulty of processing, is expected to solve some difficult problems that present thickened oil recovery process is faced.Existing scholar carries out the test of downhole catalytic reforming at the thickened oil recovery scene, and obtains initial success, but also exists many technical problems to need to solve.The key that this technology is succeedd is a selection of catalysts.Research at present is maximum, and effect is preferably transition metal salt solution, generally participates in reaction with ionic species.
Summary of the invention
The object of the present invention is to provide a kind of catalyst that is used for downhole catalytic reforming of viscous crude, it is a kind of colloidal solution of transition metal, and viscous crude is had certain catalytic action, and the heavy component asphalt content descends in the viscous crude of reaction back, viscosity reduces, the lighting of viscous crude part.
The concrete technical scheme that realizes the object of the invention is:
A kind of catalyst that is used for downhole catalytic reforming of viscous crude, this catalyst are a kind of colloidal solution of transition metal, and its solute is the colloidal solid of transition metal hydrous oxide, and solvent is a water; The colloidal solution of described transition metal is to adopt following steps to make: transition metal salt is dissolved in the water, in transition metal salt solution, add citric acid, the quality ratio of its transition metal salt and citric acid is 0.1～5.0, at room temperature stirred 1～4 hour, after the ethanol dilution with 1.0～20.0 times of transition metal salt solution volumes, ultrasonic oscillation 0.5～2.0 hour, the colloidal solution of transition metal; Or it is transition metal salt is soluble in water, adopt concentrated ammonia liquor that transition metal salt is precipitated, precipitation is washing after filtration, after removing heteroion, adding and transition metal ions molar ratio are 0.02～3.0 acid, heating while stirring makes its peptization, and heating and temperature control gets the colloidal solution of transition metal at 100～150 ℃; Wherein, described transition metal is a kind of of iron, cobalt, molybdenum, zinc, copper, nickel or chromium; The solid content of the colloidal solution of described transition metal is less than 25wt%; Dissolve described transition metal salt institute water consumption: the quality ratio of transition metal salt and water is 0.001～0.95; Dilute used concentration of alcohol greater than 95%.
Described acid is nitric acid, sulfuric acid or hydrochloric acid.
The present invention has certain catalytic action to viscous crude, and reaction back viscosity of thickened oil reduces, and the heavy component asphalt content descends, the lighting of viscous crude part.
The specific embodiment
Embodiment 1
Get 5.0gFeCl
36H
2O, be dissolved in the 0.5ml water, in metal salt solution, add the 1.0g citric acid, at room temperature stir and obtained red colloid in 1.0 hours, after ethanol (concentration is greater than the 95%) dilution with 5 times of colloid volumes, ultrasonic oscillation promptly obtained dispersing iron oxide colloidal solution in 1.5 hours, and measuring solid content is 2.42%.
Embodiment 2
Get 10gCoCl
26H
2O is dissolved in the 8ml water, adds the 50g citric acid in metal salt solution, at room temperature stir and got colloidal solution in 2 hours, after ethanol (concentration is greater than the 95%) dilution with 10 times of colloidal solution volumes, ultrasonic oscillation promptly got dispersion cobalt oxide colloidal solution in 2.0 hours, and measuring solid content is 7.31%.
Embodiment 3
Get 40gNi (NO
3)
26H
2O is dissolved in the 10ml water, adds the 80g citric acid in metal salt solution, at room temperature stir and got colloidal solution in 2 hours, after the ethanol dilution with 20 times of colloidal solution volumes, ultrasonic oscillation promptly got and disperses nickel oxide colloidal solution in 0.5 hour, and measuring solid content is 5.29%.
Embodiment 4
Get 40gAl
2(NO
3)
36H
2O, soluble in water, to wherein adding the concentrated ammonia liquor precipitation, precipitation is washing after filtration under the stirring state, behind the removal heteroion, adds 1ml red fuming nitric acid (RFNA) (concentration 63%), and heating is heated under 100 ℃ while stirring, obtains dispersed alumina colloidal solution.
When the present invention used, required geological conditions was: the oil reservoir oil saturation is greater than 20%; Reservoir permeability is greater than 0.8 μ m
2Sand content does not have obvious vapour and scurries less than 3%.Do not changing under the thermal recovery technology prerequisite, adopting prepad fluid slug injection mode, the solid masses content of catalyst solution is 0.001%～2.0%, and catalyst amount is 0.03 with the mass percent value of handling oil mass.The injection flow process of catalyst: prepad fluid, catalyst solution, steam.Prepad fluid adopts clear water usually.
Adopt artificial ground of the present invention to do following test:
Test 1:
Add the dispersing iron oxide colloidal solution (pressing solid masses) of Shengli Oil Field viscous crude, water and embodiment 1 preparation in autoclave, mass ratio is 100: 10: 0.15, is warming up to 240 ℃, reacts 24 hours.Adopt Brookfield flow graph viscosity of thickened oil before and after 80 ℃ of following assaying reactions to change, the variation of viscous crude medium pitch matter content before and after the normal heptane method assaying reaction.
Test 2:
In autoclave, add the dispersion cobalt oxide colloidal solution (pressing solid masses) of 100g Shengli Oil Field viscous crude, 20g water and 0.10g embodiment 2 preparations, be warming up to 220 ℃, reacted 2 days.Adopt Brookfield flow graph viscosity of thickened oil before and after 80 ℃ of following assaying reactions, the variation of viscous crude medium pitch matter content before and after the normal heptane method assaying reaction.
Test 3:
In autoclave, add the dispersion nickel oxide colloidal solution (pressing solid masses) of 100g Shengli Oil Field viscous crude, 25g water and 2.0g embodiment 3 preparations, be warming up to 280 ℃, reacted 10 days.Adopt Brookfield flow graph viscosity of thickened oil before and after 80 ℃ of following assaying reactions to change, the variation of viscous crude medium pitch matter content before and after the normal heptane method assaying reaction.
Table 1 transition metal colloidal sol catalyst catalytic performance tables of data
* in the table: reducing thick oil viscosity rate=(μ
Before-μ
After)/μ
Before* 100%, in the formula: μ
BeforeBe the viscosity of viscous crude sample before reacting, μ
AfterFor reacting the viscosity of back viscous crude sample.
Claims (2)
1. a catalyst that is used for downhole catalytic reforming of viscous crude is characterized in that this catalyst is a kind of colloidal solution of transition metal, and its solute is the colloidal solid of transition metal hydrous oxide, and solvent is a water; The colloidal solution of described transition metal is to adopt following steps to make: transition metal salt is dissolved in the water, in transition metal salt solution, add citric acid, the quality ratio of its transition metal salt and citric acid is 0.1～5.0, at room temperature stirred 1～4 hour, after the ethanol dilution with 1.0～20.0 times of transition metal salt solution volumes, ultrasonic oscillation 0.5～2.0 hour, the colloidal solution of transition metal; Or it is transition metal salt is soluble in water, adopt concentrated ammonia liquor that transition metal salt is precipitated, precipitation is washing after filtration, after removing heteroion, adding and transition metal ions molar ratio are 0.02～3.0 acid, heating while stirring makes its peptization, and heating and temperature control gets the colloidal solution of transition metal at 100～150 ℃; Wherein, described transition metal is a kind of of iron, cobalt, molybdenum, zinc, copper, nickel or chromium; The solid content of the colloidal solution of described transition metal is less than 25wt%; Dissolve described transition metal salt institute water consumption: the quality ratio of transition metal salt and water is 0.001～0.95; Dilute used concentration of alcohol greater than 95%.
2. catalyst according to claim 1 is characterized in that described acid is nitric acid, sulfuric acid or hydrochloric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100264715A CN100391601C (en) | 2006-05-11 | 2006-05-11 | Catalyst for downhole catalytic reforming of viscous crude |
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| CNB2006100264715A CN100391601C (en) | 2006-05-11 | 2006-05-11 | Catalyst for downhole catalytic reforming of viscous crude |
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| CN100391601C true CN100391601C (en) | 2008-06-04 |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100443562C (en) * | 2006-10-13 | 2008-12-17 | 中国地质大学（武汉） | Process for preparing thick oil hydrothermally catalytic cracking viscosity reducer containing amphiphilic structure |
| CN101134893A (en) * | 2007-10-16 | 2008-03-05 | 中国地质大学（武汉） | Preparation method of catalytic thinner for viscous crude water thermo-cracking |
| CN101737025B (en) * | 2008-11-20 | 2013-04-24 | 中国石油化工股份有限公司 | Method for reducing viscosity of crude oil |
| CN102287174B (en) * | 2011-04-30 | 2014-02-19 | 胜利油田胜利勘察设计研究院有限公司 | Cracking viscosity reducing method and device for oil field ground collected and conveyed salt-containing thick oil |
| CN103418437A (en) * | 2012-05-17 | 2013-12-04 | 中国石油化工股份有限公司 | Amphiphilic catalytic viscosity reducer for thickened oil aqua-thermolysis and preparation method thereof |
| CN103386323B (en) * | 2013-08-07 | 2015-01-14 | 中国海洋石油总公司 | Quality-improving and viscosity-reducing catalyst and preparation method thereof |
| CN103480424B (en) * | 2013-09-22 | 2016-09-14 | 东北石油大学 | A kind of for the upgrading viscosity reduction preparation method and applications of ultra-dispersed catalyst |
| CN106008612B (en) * | 2016-06-01 | 2018-07-10 | 中国石油天然气股份有限公司 | Binuclear cobalt compound and application thereof in underground catalytic modification and viscosity reduction of thickened oil |
| CN107880866B (en) * | 2017-05-23 | 2021-03-23 | 西南石油大学 | Heavy oil in-situ catalytic modified metal nanocrystalline viscosity reducer and preparation method thereof |
| CN108276980B (en) * | 2018-02-06 | 2020-09-29 | 西南石油大学 | Method for preparing thickened oil oxidation catalyst by using biomass as raw material |
| CN116023921B (en) * | 2021-10-25 | 2024-07-19 | 中国石油化工股份有限公司 | Catalyst for in-situ modification of thickened oil and catalytic hydrothermal cracking combined method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5951981A (en) * | 1982-09-18 | 1984-03-26 | Asahi Chem Ind Co Ltd | Production of light oil from heavy hydrocarbon oil |
| US4846274A (en) * | 1986-11-17 | 1989-07-11 | Ensci, Incorporated | Process for recovering hydrocarbon |
| US5916432A (en) * | 1997-09-24 | 1999-06-29 | Alberta Oil Sands Technology And Research Authority | Process for dispersing transition metal catalytic particles in heavy oil |
| CN1252486A (en) * | 1999-11-22 | 2000-05-10 | 丁焰 | Petroleum recovering method and equipment through microwave cracking into light hydrocarbon |
-
2006
- 2006-05-11 CN CNB2006100264715A patent/CN100391601C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5951981A (en) * | 1982-09-18 | 1984-03-26 | Asahi Chem Ind Co Ltd | Production of light oil from heavy hydrocarbon oil |
| US4846274A (en) * | 1986-11-17 | 1989-07-11 | Ensci, Incorporated | Process for recovering hydrocarbon |
| US5916432A (en) * | 1997-09-24 | 1999-06-29 | Alberta Oil Sands Technology And Research Authority | Process for dispersing transition metal catalytic particles in heavy oil |
| CN1252486A (en) * | 1999-11-22 | 2000-05-10 | 丁焰 | Petroleum recovering method and equipment through microwave cracking into light hydrocarbon |
Non-Patent Citations (4)
| Title |
|---|
| Theoretical modeling of molecular interactions of iron withasphaltenes from heavy crude oil. Sergio Rosales et al.Journal of Molecular Catalysis A:Chemical,Vol.246 . 2005 |
| Theoretical modeling of molecular interactions of iron withasphaltenes from heavy crude oil. Sergio Rosales et al.Journal of Molecular Catalysis A:Chemical,Vol.246 . 2005 * |
| 井下降粘开采稠油技术研究. 范洪富等.石油与天然气化工，第30卷第1期. 2001 |
| 井下降粘开采稠油技术研究. 范洪富等.石油与天然气化工，第30卷第1期. 2001 * |
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