CN103418437A - Amphiphilic catalytic viscosity reducer for thickened oil aqua-thermolysis and preparation method thereof - Google Patents
Amphiphilic catalytic viscosity reducer for thickened oil aqua-thermolysis and preparation method thereof Download PDFInfo
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- CN103418437A CN103418437A CN201210153927XA CN201210153927A CN103418437A CN 103418437 A CN103418437 A CN 103418437A CN 201210153927X A CN201210153927X A CN 201210153927XA CN 201210153927 A CN201210153927 A CN 201210153927A CN 103418437 A CN103418437 A CN 103418437A
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Abstract
The invention discloses an amphiphilic catalytic viscosity reducer for thickened oil aqua-thermolysis and a preparation method thereof. The viscosity reducer is prepared by metathesis reactions between following materials in parts by weight: 0.5 to 50 parts of nickel salt, 5 to 200 parts of aromatic ring acid, and 100 parts of distilled water, wherein the nickel salt is nickel nitrate, nickel sulfate, or nickel chloride, and the aromatic ring acid is benzoic acid, sulfonic acid, toluene-4-sulfonic acid, or p-toluenesulfonic acid. The amphiphilic catalysis viscosity reducer for thickened oil aqua-thermolysis is capable of catalyzing thickened oil aqua-thermolysis reactions at a lower temperature (not larger than 200 DEG C), largely reduces the viscosity of the thickened oil after reactions, the viscosity-reducing rate being over 85%, and has the excellent characteristics of simple preparation technology, high universality, and good viscosity-reducing effect.
Description
Technical field
The present invention relates to the thickened oil recovery field, furtherly, relate to a kind of thick oil hydrothermal cracking parental type catalytic thinner and preparation method thereof.
Background technology
Viscous crude is a kind of unconventional hydrocarbon resources had a high potential.China is one of the world four large viscous crude state, and the viscous crude resource is very abundant, and how Efficient Development and utilize the viscous crude resource, become the petroleum industry urgent problem.Developed some thickened oil recovery methods both at home and abroad, wherein steam soak and steam flooding are to adopt in the world at present the most general recovery method.Although the method is fine to the exploitation effect of common heavy oil, very limited to the exploitation effect of the super viscous crude of spy.The hydrothermal cracking and catalyzing reaction has brought the new approaches of special super heavy oil recovery, it is in steam injection, also give catalyst and other auxiliary agent that oil reservoir is suitable, make the heavy component in special super viscous crude realize catalytic pyrolysis under hydrothermal condition, irreversibly reduce viscosity of thickened oil, improve to a certain extent the quality of viscous crude, thereby make its reduced viscosity and be easy to extraction, there is wide development prospect.At present, utilize the special super viscous crude of this technology exploitation to become the focus that people pay close attention to.
The key of this technology is the development of hydrothermal catalytic cracking viscosity depressant, the thick oil hydrothermal catalyst can be summarized as following a few class at present: (1) high price transition metal ions water-soluble catalyst, be characterized in easily injecting stratum, but poor with the contact of viscous crude, and easily be plucked out of while producing.(2) oil-soluble transition metal compound catalyst, be characterized in more difficult injection stratum.(3) solid super-strong acid and heteropolyacid catalyst, after it meets water, catalytic activity reduces.And at present some hydrothermal catalytic cracking viscosity depressants of bibliographical information exist serviceability temperature higher (being more than or equal to 240 ℃), and with the poor shortcoming of crude oil contact, be difficult to on-the-spot large-scale promotion application.So develop the viscosity reduction catalyst that is applicable to the stratum lower temperature and can fully contacts with oil and be can the march toward key of extensive field popularization application of hydrothermal catalytic cracking technology.
Summary of the invention
For solving problems of the prior art, the invention provides a kind of thick oil hydrothermal cracking parental type catalytic thinner and preparation method thereof.Be applicable to be less than or equal under 200 ℃ of temperature conditions, should inject stratum, and can fully contact with the super viscous crude of spy and make viscous crude generation cracking after entering stratum, viscosity reducing effect be good, and raw material sources are extensive, and preparation technology is simple, pollution-free.
One of purpose of the present invention is to provide a kind of thick oil hydrothermal cracking parental type catalytic thinner.
Described catalytic thinner is to comprise that the following material in parts by weight obtains through reduction reaction:
Nickel salt 0.5-50 weight portion, preferably 5 ~ 20 weight portions
Aromatic ring acid 5-200 weight portion, preferably 40 ~ 125 weight portions
Distilled water 100 weight portions
Described nickel salt is nickel nitrate, nickelous sulfate or nickel chloride;
Aromatic ring acid is benzoic acid, sulfonic acid, toluene-4-sulfonic acid or p-methyl benzenesulfonic acid.
Described catalytic thinner is to be prepared by the method comprised the following steps:
1) aromatic ring acid is dropped under 40～60 ℃ and stirs heating water bath, pass into nitrogen, slowly drip with the water-soluble nickel salt solution of distillation, be warming up to 70～110 ℃, react 4～5 hours;
2) make described thick oil hydrothermal cracking parental type catalytic thinner after washing after filtration,, drying.
Two of purpose of the present invention is to provide a kind of preparation method of thick oil hydrothermal cracking parental type catalytic thinner.
Comprise:
1) aromatic ring acid is dropped under 40～60 ℃ and stirs heating water bath, pass into nitrogen, slowly drip with the water-soluble nickel salt solution of distillation, be warming up to 70～110 ℃, react 4～5 hours,
2) make described thick oil hydrothermal cracking parental type catalytic thinner after washing after filtration,, drying.
Specifically can adopt following steps:
1) choosing of raw material: nickel salt: 0.5 ~ 50 weight portion; Aromatic ring acid: 5 ~ 200 weight portions; Distilled water: 100 weight portions, standby;
2) aromatic ring acid is added drop-wise in three-necked bottle, passes into high pure nitrogen, under 40～60 ℃, stir heating water bath, slowly drip nickel salt solution, be warming up to 70～110 ℃, react 4～5 hours,
3) make described thick oil hydrothermal cracking parental type catalytic thinner after washing after filtration,, drying; In preferably distilled water washing, the vacuum of 80～110 ℃ dry 24～48 hours.
Application: this is placed in to autoclave for thick oil hydrothermal cracking parental type catalytic thinner, water and viscous crude, reaction temperature is 200 ℃, and the reaction time is 24～48h, and oil-water ratio is 7:3, the catalytic thinner dosage is 0.1～0.6%(weight), after reaction, viscosity break ratio reaches more than 85%.
The invention has the beneficial effects as follows:
The parental type catalytic thinner that adopts the present invention to obtain, its structure comprises the organic acid ion of metal ion and amphiphilic structure, and the aliphatic alkyl chain on its anion is lipophilic group, is soluble in the viscous crude component, there is the sulfonic acid hydrophilic radical on structure simultaneously, carry the nickel ion with catalysis.The amphiphilic structure of its catalyst promotes that nickel ion fully contacts with heavy component asphalitine, colloid in oil phase, and the activity of reaction reaches and selectively is improved.Parents' catalyst makes nickel ion be dispersed in uniformly in oil phase, form the emulsion catalyst system and catalyzing, catalyst is dispersed in the emulsion drop surface uniformly, the lipophilic group of catalyst is dissolved in viscous crude simultaneously, give full play to its catalysis, (be less than or equal to 200 ℃) at lower temperature the thick oil hydrothermal catalytic cracking reaction occurs.The heavy component generation cracking of viscous crude, the content of asphalitine and colloid reduces, and the content of light components saturated hydrocarbons and aromatic hydrocarbons increases, and bitum molecular weight reduces (amplitude reaches 25%～40%) greatly.The viscosity of reacted viscous crude reduces greatly, and viscosity break ratio reaches more than 85%, and hydrogen-to-carbon ratio (NH/NC) improves, and the quality of viscous crude obtains improvement to a certain extent.And of the present inventionly for thick oil hydrothermal cracking parental type catalytic thinner, have the advantages that universality is strong, viscosity reducing effect is good, and the advantage such as raw material sources are extensive, and preparation technology is simple, pollution-free, have broad application prospects.
The specific embodiment
Below in conjunction with embodiment, further illustrate the present invention.
Embodiment 1:
For thick oil hydrothermal cracking parental type catalytic thinner and preparation method thereof, it comprises the steps:
1) choosing of raw material: press nickel salt: 0.6 weight portion; Distilled water: 100 weight portions; Aromatic ring acid: 8 weight portions.Described nickel salt is nickel nitrate, analyzes purely, and Beijing chemical reagent Co., Ltd of Jin Hui the Pacific-Asian produces; Described aromatic ring acid is benzoic acid, analyzes purely, and Langfang Peng Cai Fine Chemical Co., Ltd produces.
2) benzoic acid is added drop-wise in three-necked bottle, pass into high pure nitrogen, stir heating water bath under 50 ℃, slowly drip nickel salt solution, be warming up to 80 ℃, isothermal reaction 4.5 hours, after filtration, in distilled water washing, the vacuum of 90 ℃ dry 36 hours, obtain for thick oil hydrothermal cracking parental type catalytic thinner.
The application: will prepare for thick oil hydrothermal cracking parental type catalytic thinner, water and Shengli Oil Field viscous crude (oily pound sign: single 56-13-19) be placed in autoclave, reaction temperature is 200 ℃, reaction time is 24h, oil-water ratio is 7:3, the catalytic thinner dosage is 0.2%(weight), after reaction, viscosity break ratio reaches more than 85%.
Embodiment 2:
For thick oil hydrothermal cracking parental type catalytic thinner and preparation method thereof, it comprises the steps:
1) choosing of raw material: press nickel salt: 12 weight portions; Distilled water: 100 weight portions; Aromatic ring acid: 100 weight portions.Described nickel salt is nickelous sulfate, analyzes purely, and the Xiao Xian of Anhui Province chemical reagent factory is produced; Described aromatic ring acid is sulfonic acid, technical grade, Earthquake of Anyang station in Henan petrochemical iy produced.
2) sulfonic acid is added drop-wise in three-necked bottle, pass into high pure nitrogen, stir heating water bath under 55 ℃, slowly drip nickel salt solution, be warming up to 70 ℃, isothermal reaction 5 hours, after filtration, in distilled water washing, the vacuum of 80 ℃ dry 48 hours, obtain for thick oil hydrothermal cracking parental type catalytic thinner.
The application: will prepare for thick oil hydrothermal cracking parental type catalytic thinner, water and Shengli Oil Field viscous crude (oily pound sign: single 56-13-19) be placed in autoclave, reaction temperature is 200 ℃, reaction time is 36h, oil-water ratio is 7:3, the catalytic thinner dosage is 0.3%(weight), after reaction, viscosity break ratio reaches more than 85%.
Embodiment 3:
For thick oil hydrothermal cracking parental type catalytic thinner, it comprises the steps:
1) choosing of raw material: press nickel salt: 25 weight portions; Distilled water: 100 weight portions; Aromatic ring acid: 113 weight portions.Described nickel salt is nickel chloride, analyzes purely, and Beijing Century orient chemical Co., Ltd produces; Described aromatic ring acid is toluene-4-sulfonic acid, analyze pure, Guangzhou West Gansu Province Chemical Manufacture.
2) toluene-4-sulfonic acid is added drop-wise in three-necked bottle, pass into high pure nitrogen, stir heating water bath under 60 ℃, slowly drip nickel salt solution, be warming up to 70 ℃, isothermal reaction 4 hours, after filtration, in distilled water washing, the vacuum of 90 ℃ dry 24 hours, obtain for thick oil hydrothermal cracking parental type catalytic thinner.
The application: will prepare for thick oil hydrothermal cracking parental type catalytic thinner, water and Shengli Oil Field viscous crude (oily pound sign: single 56-13-19) be placed in autoclave, reaction temperature is 200 ℃, reaction time is 48h, oil-water ratio is 7:3, the catalytic thinner dosage is 0.35%(weight), after reaction, viscosity break ratio reaches more than 85%.
Embodiment 4:
For thick oil hydrothermal cracking parental type catalytic thinner and preparation method thereof, it comprises the steps:
1) choosing of raw material: press nickel salt: 38 weight portions; Distilled water: 100 weight portions; Aromatic ring acid: 166 weight portions.Described nickel salt is nickel chloride, analyzes purely, and Beijing Century orient chemical Co., Ltd produces; Described aromatic ring acid is sulfonic acid, technical grade, Nanjing, Nanjing petrochemical iy produced.
2) sulfonic acid is added drop-wise in three-necked bottle, pass into high pure nitrogen, stir heating water bath under 55 ℃, slowly drip nickel salt solution, be warming up to 75 ℃, isothermal reaction 4.5 hours, after filtration, in distilled water washing, the vacuum of 85 ℃ dry 48 hours, obtain for thick oil hydrothermal cracking parental type catalytic thinner.
The application: will prepare for thick oil hydrothermal cracking parental type catalytic thinner, water and Shengli Oil Field viscous crude (oily pound sign: single 56-13-19) be placed in autoclave, reaction temperature is 200 ℃, reaction time is 24～48h, oil-water ratio is 7:3, the catalytic thinner dosage is 0.4%(weight), after reaction, viscosity break ratio reaches more than 85%.
Embodiment 5:
For thick oil hydrothermal cracking parental type catalytic thinner and preparation method thereof, it comprises the steps:
1) choosing of raw material: press nickel salt: 49 weight portions; Distilled water: 100 weight portions; Aromatic ring acid: 198 weight portions.Described nickel salt is nickel nitrate, analyzes purely, and Beijing chemical reagent Co., Ltd of Jin Hui the Pacific-Asian produces; Described aromatic ring acid is p-methyl benzenesulfonic acid, analyzes purely, and Beijing Peng Cai Fine Chemical Co., Ltd produces.
2) p-methyl benzenesulfonic acid is added drop-wise in three-necked bottle, pass into high pure nitrogen, stir heating water bath under 60 ℃, slowly drip nickel salt solution, be warming up to 85 ℃, isothermal reaction 5 hours, after filtration, in distilled water washing, the vacuum of 95 ℃ dry 36 hours, obtain for thick oil hydrothermal cracking parental type catalytic thinner.
The application: will prepare for thick oil hydrothermal cracking parental type catalytic thinner, water and Shengli Oil Field viscous crude (oily pound sign: single 56-13-19) be placed in autoclave, reaction temperature is 200 ℃, reaction time is 24h, oil-water ratio is 7:3, the catalytic thinner dosage is 0.35%(weight), after reaction, viscosity break ratio reaches more than 85%.
Claims (4)
1. a thick oil hydrothermal cracking parental type catalytic thinner is characterized in that:
Described catalytic thinner is to comprise that the following material in parts by weight obtains through metathesis reaction:
Nickel salt 0.5 ~ 50 weight portion
Aromatic ring acid 5 ~ 200 weight portions
Distilled water 100 weight portions
Described nickel salt is nickel nitrate, nickelous sulfate or nickel chloride;
Aromatic ring acid is benzoic acid, sulfonic acid, toluene-4-sulfonic acid or p-methyl benzenesulfonic acid.
2. thick oil hydrothermal cracking parental type catalytic thinner as claimed in claim 1 is characterized in that:
Nickel salt 5 ~ 20 weight portions
Aromatic ring acid 40 ~ 125 weight portions.
3. thick oil hydrothermal cracking parental type catalytic thinner as claimed in claim 1 is characterized in that:
Described catalytic thinner is to be prepared by the method comprised the following steps:
1) aromatic ring acid is dropped under 40～60 ℃ and stirs heating water bath, pass into nitrogen, slowly drip with the water-soluble nickel salt solution of distillation, be warming up to 70～110 ℃, react 4～5 hours;
2) make described thick oil hydrothermal cracking parental type catalytic thinner after washing after filtration,, drying.
4. the preparation method of a thick oil hydrothermal cracking parental type catalytic thinner as described as one of claim 1 ~ 3 is characterized in that described method comprises:
1) aromatic ring acid is dropped under 40～60 ℃ and stirs heating water bath, pass into nitrogen, slowly drip with the water-soluble nickel salt solution of distillation, be warming up to 70～110 ℃, react 4～5 hours;
2) make described thick oil hydrothermal cracking parental type catalytic thinner after washing after filtration,, drying.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105349129A (en) * | 2015-10-28 | 2016-02-24 | 中国石油大学(华东) | Heavy oil hydrothermal catalytic cracking viscosity reducer, and preparation and purification method thereof |
| CN108276980A (en) * | 2018-02-06 | 2018-07-13 | 西南石油大学 | A method of with biomass it is that raw material prepares viscous crude oxidation catalyst |
| CN109424344A (en) * | 2017-09-04 | 2019-03-05 | 中国石油化工股份有限公司 | A kind of method of bioactive molecule collaboration modification viscosity reduction heavy crude producing |
| CN115011323A (en) * | 2022-07-19 | 2022-09-06 | 胜利油田方圆化工有限公司 | Viscosity reducer for hydrothermal cracking of heavy oil and preparation method and application thereof |
| CN115873576A (en) * | 2023-01-03 | 2023-03-31 | 南阳腾远石油工程技术服务有限公司 | Thick oil viscosity reducer and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2012
- 2012-05-17 CN CN201210153927XA patent/CN103418437A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 吴川: "双亲型稠油水热裂解降粘催化剂的合成及反应机理研究", 《博士学位论文》, 15 October 2011 (2011-10-15), pages 39 - 44 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105349129A (en) * | 2015-10-28 | 2016-02-24 | 中国石油大学(华东) | Heavy oil hydrothermal catalytic cracking viscosity reducer, and preparation and purification method thereof |
| 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 |
| CN109424344A (en) * | 2017-09-04 | 2019-03-05 | 中国石油化工股份有限公司 | A kind of method of bioactive molecule collaboration modification viscosity reduction heavy crude producing |
| CN108276980A (en) * | 2018-02-06 | 2018-07-13 | 西南石油大学 | A method of with biomass it is that raw material prepares viscous crude oxidation catalyst |
| 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 |
| CN115011323A (en) * | 2022-07-19 | 2022-09-06 | 胜利油田方圆化工有限公司 | Viscosity reducer for hydrothermal cracking of heavy oil and preparation method and application thereof |
| CN115011323B (en) * | 2022-07-19 | 2023-06-02 | 胜利油田方圆化工有限公司 | Viscosity reducer for aquathermolysis of thick oil and preparation method and application thereof |
| CN115873576A (en) * | 2023-01-03 | 2023-03-31 | 南阳腾远石油工程技术服务有限公司 | Thick oil viscosity reducer and preparation method thereof |
| CN115873576B (en) * | 2023-01-03 | 2023-10-24 | 南阳腾远石油工程技术服务有限公司 | Thickened oil viscosity reducer and preparation method thereof |
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Application publication date: 20131204 |