CN101570684B - Preparation method of catalytic viscosity reducer for thick oil aqua-thermolysis - Google Patents
Preparation method of catalytic viscosity reducer for thick oil aqua-thermolysis Download PDFInfo
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- CN101570684B CN101570684B CN2007103072162A CN200710307216A CN101570684B CN 101570684 B CN101570684 B CN 101570684B CN 2007103072162 A CN2007103072162 A CN 2007103072162A CN 200710307216 A CN200710307216 A CN 200710307216A CN 101570684 B CN101570684 B CN 101570684B
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- molybdenum
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Abstract
The invention relates to a preparation method of a catalytic viscosity reducer for thick oil aqua-thermolysis, which can reduce the viscosity of the thick oil. The preparation method comprises the following steps: 1) molybdate, distilled water, aqueous alkali and aromatic acid are selected as raw materials for standby use, and the ratio of the molybdate, distilled water, aqueous alkali with concentration being 1-5mol/L and aromatic acid is 1-2g: 10-20mL: 8-10mL: 15-30mL; 2) the molybdate is dissolved into the distilled water; the water bath is stirred under the temperature of 80-120 DEG C andis heated, the aqueous alkali is dropwise added slowly, the pH value is adjusted from 9 to 14 and reaction lasts for 15min-60min; aromatic acid is dropwise added slowly and reacts for 4-6 hours under constant temperature, and then is distilled to remove water to obtain the catalytic viscosity reducer for thick oil aqua-thermolysis. The invention has the advantages of strong universality, good viscosity reduction effect and simply preparing technology.
Description
Technical field
The present invention relates to a kind of preparation method that the thick oil hydrothermal cracked reduces the viscosity-depression agent of viscosity of thickened oil that is used for.
Background technology
The notion of hydrothermal cracking reaction is proposed by people such as Canadian scientist Hyne the earliest nineteen eighty-three, they find that series reaction such as desulfurization, denitrogenation, hydrogenation, open loop and water-gas shift take place the viscous crude in the oil-sand under the effect of high-temperature vapor, and these reactions are referred to as the hydrothermal cracking reaction.
Subsequently, Hyne and co-worker's comparative study thereof metal ions such as nickel, molybdenum, copper, zinc, manganese and iron under simulation steam treatment condition, to the katalysis of Canada and Venezuela's thick oil hydrothermal scission reaction.Rivas etc. as the steam-assisted recovery processing additive, find that the nickel salt additive can increase gas production rate, reduces the viscosity of viscous crude with transition metal salt solution.Clark etc. utilize water and transition-metal catalyst modified pitch matter crude oil, found that water base Fe (II) additive can stop by coupling reaction generates insoluble product, and might promote that H shifts between organism, water base nail (III) additive can promote the C-S bond rupture.Richard etc. have introduced a kind of oil-soluble catalyst (heptane molybdenum ammonium formiate) in its literary composition, can be used for the ground upgrading of heavy crude.Patent US 5209295 and US 5314615 have reported with transition-metal catalyst and have fallen glutinous method in the cracking of underground realization thick oil hydrothermal that this method can change the chemical structure of crude oil, improves the flowability of viscous crude, improves oil recovery factor.
Domestic many scholars also study the thick oil hydrothermal catalytic cracking viscosity reduction, wish irreversibly to have reduced the viscosity of viscous crude, thereby improve crude oil greatly in the seepage effect of formation pore and the flowability in conveying pipe, thereby can significantly improve recovery ratio and make things convenient for the collection under the normal temperature condition defeated, Liu Yongjian, people such as Fan Hongfu select transition metal salt, transition metal salt complex and transition metal salt colloidal dispersion system have carried out the test in place of hydrothermal catalytic cracking to Liaohe River viscous crude as catalyzer, and obtained certain success, but still also have problems to need to solve.The core of reducing viscosity in hydrothermal cracking and catalyzing thick oil repercussion study is the development of catalytic thinner, the screening or development cost is low, activity is the key of hydrothermal cracking upgrading viscous crude with selectivity height, reaction conditions serial catalytic thinner wide, that be applicable to different viscous crude.
At present catalytic thinner to general spy, super reducing thick oil viscosity effect obvious [described special viscous crude be meant viscosity be higher than 10,000, the be less than or equal to 50,000 mPaS viscous crude of (50 ℃); Described super viscous crude is meant that viscosity is the viscous crude greater than 50,000 mPaS (50 ℃)], but relatively poor greater than the super reducing thick oil viscosity effect of 300,000 mPaS (50 ℃) to viscosity, promptly universality is poor.
Summary of the invention
The object of the present invention is to provide the preparation method that a kind of universality is strong, viscosity reducing effect good, preparation technology simply is used for thick oil hydrothermal cracked catalytic thinner.
To achieve these goals, technical scheme of the present invention is: be used for the preparation method of thick oil hydrothermal cracked catalytic thinner, it is characterized in that it comprises the steps:
1) choosing of raw material: by molybdenum salt: distilled water: concentration is the alkaline solution of 1～5mol/L: aromatic ring acid=1～2 gram: 10～20mL: 8～10mL: 15～30mL, choose molybdenum salt, distilled water, alkaline solution and aromatic ring acid starting material, and standby;
2) molybdenum salt is dissolved in the distilled water, stirs heating in water bath down at 80～120 ℃, slowly drip alkaline solution, regulating the pH value is 9～14, reaction 15min-60min; Slowly drip aromatic ring acid then, isothermal reaction 4～6h, dephlegmate both must be used for thick oil hydrothermal cracked catalytic thinner.
Described molybdenum salt is nitric acid molybdenum, molybdenum trisulfate, ammonium molybdate, Sodium orthomolybdate or molybdic oxide.
Described alkaline solution is potassium hydroxide solution, sodium hydroxide solution, aqua calcis, sodium carbonate solution or solution of potassium carbonate.
Described aromatic ring acid is Witco 1298 Soft Acid.
Use: this is used for thick oil hydrothermal cracked catalytic thinner, water and viscous crude places autoclave, temperature of reaction is 180～280 ℃, and the reaction times is 24～48h, and O/W is 7: 3, the catalytic thinner dosage is 0.07～0.2% (weight), and reaction back viscosity break ratio can reach more than 90%.
The invention has the beneficial effects as follows:
1, the thick oil hydrothermal cracked catalytic thinner that is used for of the present invention not only has reasonable viscosity reducing effect to general spy, super viscous crude, and viscosity is had obvious catalytic viscosity reduction effect greater than the super viscous crude of 300,000 mPaS (50 ℃), and viscosity break ratio all reaches more than 90%; The thick oil hydrothermal cracked catalytic thinner that is used for of the present invention has the advantages that universality is strong, viscosity reducing effect is good.
2, the thick oil hydrothermal cracked catalytic thinner that is used for of the present invention makes the colloid of viscous crude, bituminous matter that scission reaction take place, the macromolecular heavy component of part has changed into micromolecular stable hydrocarbon, aromatic hydrocarbon, variation has to a certain degree taken place in the state of aggregation of viscous crude molecule simultaneously, the amount that generates small molecules stable hydrocarbon and aromatic hydrocarbon increases, heteroatoms in bituminous matter, the colloid reduces, weakened the interaction force between the molecule, hydrogen-to-carbon ratio (N
H/ N
C) improve, super viscous crude quality obtains improvement to a certain degree.The viscosity of viscous crude further reduces.
3, raw material sources of the present invention are extensive, and preparation technology is simple, and energy-conserving and environment-protective are pollution-free, meet the needs (viscous oil recovery become energy development emphasis that Eleventh-Five Year Plan dispose) of national economic development to the energy, and its market outlook are inestimable.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
Embodiment 1:
Be used for the preparation method of thick oil hydrothermal cracked catalytic thinner, it comprises the steps:
1) choosing of raw material: by molybdenum salt: distilled water: concentration is the alkaline solution of 1mol/L: Witco 1298 Soft Acid=1 gram: 10mL: 8mL: 15mL, choose molybdenum salt, distilled water, alkaline solution and Witco 1298 Soft Acid raw material, and standby; Described molybdenum salt is the nitric acid molybdenum, and described alkaline solution is a sodium hydroxide solution;
2) molybdenum salt is dissolved in the distilled water, stirs heating in water bath down at 80 ℃, slowly drip alkaline solution, regulating the pH value is 9, reaction 15min; Slowly drip Witco 1298 Soft Acid then, constant temperature (80 ℃) reaction 4h, dephlegmate both must be used for thick oil hydrothermal cracked catalytic thinner.
Embodiment 2:
Be used for the preparation method of thick oil hydrothermal cracked catalytic thinner, it comprises the steps:
1) choosing of raw material: by molybdenum salt: distilled water: concentration is the alkaline solution of 2mol/L: Witco 1298 Soft Acid=1.5 grams: 15mL: 9mL: 20mL, choose molybdenum salt, distilled water, alkaline solution and Witco 1298 Soft Acid raw material, and standby; Described molybdenum salt is molybdenum trisulfate, and described alkaline solution is a potassium hydroxide solution;
2) molybdenum salt is dissolved in the distilled water, stirs heating in water bath down at 100 ℃, slowly drip alkaline solution, regulating the pH value is 11, reaction 20min; Slowly drip Witco 1298 Soft Acid then, constant temperature (100 ℃) reaction 5h, dephlegmate both must be used for thick oil hydrothermal cracked catalytic thinner.
Embodiment 3:
Be used for the preparation method of thick oil hydrothermal cracked catalytic thinner, it comprises the steps:
1) choosing of raw material: by molybdenum salt: distilled water: concentration is the alkaline solution of 3mol/L: Witco 1298 Soft Acid=1.8 grams: 18mL: 9mL: 25mL, choose molybdenum salt, distilled water, alkaline solution and Witco 1298 Soft Acid raw material, and standby; Described molybdenum salt is ammonium molybdate, and described alkaline solution is an aqua calcis;
2) molybdenum salt is dissolved in the distilled water, stirs heating in water bath down at 110 ℃, slowly drip alkaline solution, regulating the pH value is 12, reaction 40min; Slowly drip Witco 1298 Soft Acid then, constant temperature (110 ℃) reaction 5h, dephlegmate both must be used for thick oil hydrothermal cracked catalytic thinner.
Embodiment 4:
Be used for the preparation method of thick oil hydrothermal cracked catalytic thinner, it comprises the steps:
1) choosing of raw material: by molybdenum salt: distilled water: concentration is the alkaline solution of 5mol/L: Witco 1298 Soft Acid=2 grams: 20mL: 10mL: 30mL, choose molybdenum salt, distilled water, alkaline solution and Witco 1298 Soft Acid raw material, and standby; Described molybdenum salt is Sodium orthomolybdate, and described alkaline solution is a sodium carbonate solution;
2) molybdenum salt is dissolved in the distilled water, stirs heating in water bath down at 120 ℃, slowly drip alkaline solution, regulating the pH value is 14, reaction 60min; Slowly drip Witco 1298 Soft Acid then, constant temperature (120 ℃) reaction 6h, dephlegmate both must be used for thick oil hydrothermal cracked catalytic thinner.
Embodiment 5:
Be used for the preparation method of thick oil hydrothermal cracked catalytic thinner, it comprises the steps:
1) choosing of raw material: by molybdenum salt: distilled water: concentration is the alkaline solution of 2mol/L: Witco 1298 Soft Acid=1 gram: 20mL: 10mL: 15mL, choose molybdenum salt, distilled water, alkaline solution and Witco 1298 Soft Acid raw material, and standby; Described molybdenum salt is molybdic oxide, and described alkaline solution is a solution of potassium carbonate;
2) molybdenum salt is dissolved in the distilled water, stirs heating in water bath down at 80 ℃, slowly drip alkaline solution, regulating the pH value is 9, reaction 60min; Slowly drip Witco 1298 Soft Acid then, isothermal reaction 6h, dephlegmate both must be used for thick oil hydrothermal cracked catalytic thinner.
Claims (1)
1. the preparation method who is used for thick oil hydrothermal cracked catalytic thinner is characterized in that it comprises the steps:
1) choosing of raw material: by molybdenum salt: distilled water: concentration is the alkaline solution of 1～5mol/L: aromatic ring acid=1～2 gram: 10～20mL: 8～10mL: 15～30mL, choose molybdenum salt, distilled water, alkaline solution and aromatic ring acid starting material, and standby;
2) molybdenum salt is dissolved in the distilled water, stirs heating in water bath down at 80～120 ℃, slowly drip alkaline solution, regulating the pH value is 9～14, reaction 15min-60min; Slowly drip aromatic ring acid then, isothermal reaction 4～6h, dephlegmate promptly gets and is used for thick oil hydrothermal cracked catalytic thinner;
Described molybdenum salt is nitric acid molybdenum, molybdenum trisulfate, ammonium molybdate or Sodium orthomolybdate;
Described alkaline solution is potassium hydroxide solution, sodium hydroxide solution or aqua calcis;
Described aromatic ring acid is Witco 1298 Soft Acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007103072162A CN101570684B (en) | 2007-10-16 | 2007-12-30 | Preparation method of catalytic viscosity reducer for thick oil aqua-thermolysis |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710053558.6 | 2007-10-16 | ||
| CNA2007100535586A CN101134893A (en) | 2007-10-16 | 2007-10-16 | Preparation method of catalytic thinner for viscous crude water thermo-cracking |
| CN2007103072162A CN101570684B (en) | 2007-10-16 | 2007-12-30 | Preparation method of catalytic viscosity reducer for thick oil aqua-thermolysis |
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| CN101570684A CN101570684A (en) | 2009-11-04 |
| CN101570684B true CN101570684B (en) | 2011-11-30 |
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| CNA2007100535586A Pending CN101134893A (en) | 2007-10-16 | 2007-10-16 | Preparation method of catalytic thinner for viscous crude water thermo-cracking |
| CN2007103072162A Expired - Fee Related CN101570684B (en) | 2007-10-16 | 2007-12-30 | Preparation method of catalytic viscosity reducer for thick oil aqua-thermolysis |
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| CNA2007100535586A Pending CN101134893A (en) | 2007-10-16 | 2007-10-16 | Preparation method of catalytic thinner for viscous crude water thermo-cracking |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103421483B (en) * | 2012-05-17 | 2015-12-09 | 中国石油化工股份有限公司 | A kind of thick oil hydrothermal cracking nano-catalytic viscosity-depression agent 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 |
| CN103566978B (en) * | 2013-10-25 | 2015-12-09 | 中国地质大学（武汉） | Copper, the agent of molybdenum bimetallic center reducing viscosity in hydrothermal cracking and catalyzing thick oil and preparation method thereof |
| CN104558352B (en) * | 2013-10-28 | 2018-02-23 | 中国石油化工股份有限公司 | Block polymer and preparation method thereof and the application in thick oil hydrothermal catalytic visbreaking and the method for thick oil hydrothermal catalytic visbreaking |
| CN105349129B (en) * | 2015-10-28 | 2018-07-03 | 中国石油大学(华东) | A kind of thick oil hydrothermal catalytic cracking visbreaking agent and its preparation and purification method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4506733A (en) * | 1983-08-19 | 1985-03-26 | Alberta Oil Sands Technology And Research Authority | Additive for inclusion in a heavy oil reservoir undergoing steam injection |
| CN1843622A (en) * | 2006-05-11 | 2006-10-11 | 上海三瑞化学有限公司 | Catalyst for downhole catalytic reforming of viscous crude |
| CN1948349A (en) * | 2006-11-09 | 2007-04-18 | 西南石油大学 | Preparation method of acetyl acetone cyclodextrin inclusion compound and its application in reducing thick oil viscosity |
-
2007
- 2007-10-16 CN CNA2007100535586A patent/CN101134893A/en active Pending
- 2007-12-30 CN CN2007103072162A patent/CN101570684B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4506733A (en) * | 1983-08-19 | 1985-03-26 | Alberta Oil Sands Technology And Research Authority | Additive for inclusion in a heavy oil reservoir undergoing steam injection |
| CN1843622A (en) * | 2006-05-11 | 2006-10-11 | 上海三瑞化学有限公司 | Catalyst for downhole catalytic reforming of viscous crude |
| CN1948349A (en) * | 2006-11-09 | 2007-04-18 | 西南石油大学 | Preparation method of acetyl acetone cyclodextrin inclusion compound and its application in reducing thick oil viscosity |
Non-Patent Citations (1)
| Title |
|---|
| 刘永建等.稠油的水热裂解反应及其降粘机理.《大庆石油学院学报》.2002,第26卷(第3期),95-98. * |
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| CN101134893A (en) | 2008-03-05 |
| CN101570684A (en) | 2009-11-04 |
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