CN102492411B - Alkyl ester sulphonate complex viscosity depressant with hydrogen supply structure and preparation method thereof - Google Patents
Alkyl ester sulphonate complex viscosity depressant with hydrogen supply structure and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a viscosity depressant for aquathermolysis viscosity-reducing exploitation of thick oil and a preparation method thereof. The preparation method for the alkyl ester sulphonate complex viscosity depressant with the hydrogen supply structure is characterized by comprising the following steps: 1), performing esterification reaction in the molar mass ratio of natural fatty alcohol to formic acid of 1 to (5.0 -8.0); 2), adding the natural fatty alcohol and ethylidene dichloride in the molar mass ratio of 1 to (2.0-2.5); 3), dropping chlorosulfonic acid in the molar mass ratio of the natural fatty alcohol to the chlorosulfonic acid of 1 to (1.3-1.8) to perform sulfonation reaction for 0.5-1h, and then aging the mixture; and 4), adding the natural fatty alcohol and transition metal in the molar mass ratio of 1 to 0.12 or 1 to 0.17 to an intermediate product to perform a complex reaction for 1-2h; stewing and layering the mixture to remove the water of upper layer, and drying the mixture to obtain lower wax which is the alkyl ester sulphonate complex viscosity depressant with the hydrogen supply structure. The viscosity depressant prepared by the method has good viscosity-reducing effects at 200 DEG C, and simultaneously has the characteristics of easily acquired materials, and a simple preparation process.
Description
Technical field
The present invention relates to a kind of viscosity-depression agent for the exploitation of thick oil hydrothermal cracking viscosity reduction and preparation method thereof.
Background technology
Along with the continuous minimizing of conventional crude and the people increase day by day to petroleum demand, viscous crude is as the huge unconventional energy resource of a kind of reserves, and its exploitation more and more comes into one's own.There is abundant viscous crude resource in China, verifies and controls reserves and reached 16 * 10
8T is the world the fourth-largest viscous crude producing country after the U.S., Canada and Venezuela.Yet due to viscous crude molecular structure complexity, heavy components content is high, causes that its viscosity and zero pour are higher, flow difficulties, and existing production technique is difficult to it is exploited effectively, and the exploitation of especially special super viscous crude resource is difficult especially.
Up to now, viscous oil recovery method mainly contains thermal recovery (combustion in situ, electrically heated, steam stimulation and steam flood), biological degradation, physics viscosity reduction method and the exploitation of chemical viscosity reduction method.Wherein, hydrothermal cracking viscosity reduction production technique is a kind of new technology that is derived on the cyclic steam stimulation basis.It is that stratum is own as a cheapness, available hydrothermal cracking and catalyzing cracking reactor, in injecting steam, also give catalyzer and other auxiliary agents that oil reservoir is suitable, make the part heavy component in viscous crude realize catalytic pyrolysis under hydrothermal condition, thereby make its viscosity decrease, be easy to extraction.The method scope of application is wide, and the super viscous crude resource of spy that present steam stimulation technology is difficult to exploit also has effect preferably.
But some viscous crude is after the hydrothermal cracking and catalyzing reaction, and its viscosity is difficult to keep for a long time stable, can rebound rapidly, and has a strong impact on the exploitation effect of situ production.This is that its reunion has caused the rapid rise of viscosity because viscous crude, in reaction process, can produce many living radicals.Be subjected to the inspiration of hydrocracking technique in petroleum refining process, someone adopts hydrogen supply agent (as naphthane, methylcyclohexane, formic acid and toluene etc.) and catalytic thinner to carry out composite use, solves this problem.Hydrogen supply agent can produce a large amount of hydroperoxyl radicals, they can react with living radical, thereby suppress the reunion of living radical, can also promote the hydrogenation reaction of the unsaturated compositions such as alkene simultaneously, improve the removal efficiency of the impurity such as sulphur, nitrogen, oxygen in crude oil, prevent green coke.But in actual applications, this technology exists such as the hydrogen supply agent large usage quantity, and its best injection rate is difficult for accurately estimation, is subjected to reservoir heterogeneity to affect, be difficult to and the problems such as catalyzer fully contacts.How effectively hydrogen donor component and catalyst component to be combined, give full play to their synergistic effect, remain a difficult point needing solution in the R&D work of hydrothermal cracking and catalyzing cracking viscosity-depression agent badly.
Summary of the invention
The object of the present invention is to provide alkyl ester sulfonate complex compound viscosity-depression agent of a kind of tool hydrogen supply structure and preparation method thereof, viscosity-depression agent prepared by the method is respond well at 200 ℃ of lower viscosity reductions, has simultaneously that raw material is easy to get, the simple characteristics of preparation technology.
To achieve these goals, the technical scheme that the present invention takes is: the alkyl ester sulfonate complex compound reducing viscosity in hydrothermal cracking and catalyzing thick oil agent of tool hydrogen supply structure, the chemical name that it is characterized in that it are the alkyl ester sulfonic acid iron complex of tool hydrogen supply structure.
Described alkyl ester is by natural fatty alcohol (C12～C18) carry out esterification with formic acid to make.
Described iron is to be made by brown iron oxide or iron powder generation complex reaction.
The preparation method of the alkyl ester sulfonate complex compound viscosity-depression agent of tool hydrogen supply structure, is characterized in that it comprises the steps:
1) by natural fatty alcohol, with the molar mass ratio of formic acid, be 1: 5.0～8.0, choose natural fatty alcohol and formic acid, join in container (as there-necked flask), be heated to 70～90 ℃ and carry out esterification 1～2h, obtain alkyl ester;
2) by natural fatty alcohol, with the molar mass ratio of ethylene dichloride, be 1: 2.0～2.5, choose ethylene dichloride, join (ethylene dichloride is dissolved in alkyl ester in container) in described container;
3) described container is positioned in ice-water bath, by natural fatty alcohol, with the molar mass ratio of chlorsulfonic acid, be 1: 1.3～1.8, choose chlorsulfonic acid, to at the uniform velocity dripping chlorsulfonic acid in container, carry out sulfonation reaction, sulfonation 0.5～1h, after sulfonation completes, be warming up to 70～90 ℃ of aging 1～2h, obtain intermediate product;
4) by natural fatty alcohol, with the molar mass ratio of transition metal, be 1: 0.12 (iron powder) or 1: 0.17 (brown iron oxide), choose transition metal, carry out complex reaction at 100～120 ℃, transition metal being joined to intermediate product, reaction 1～2h; Stratification after reaction finishes, remove the water on upper strata, and after drying, lower floor's wax is the alkyl ester sulfonate complex compound viscosity-depression agent (can be used for the reducing thick oil viscosity exploitation) of tool hydrogen supply structure under 60 ℃.
Described natural fatty alcohol is one or two or more kinds mixture by any proportioning in lauryl alcohol (C12), tetradecyl alcohol (C14), palmityl alcohol (C16), stearyl alcohol (C18).
Described transition metal is any one in iron powder, brown iron oxide; When transition metal was iron powder, the molar mass ratio of natural fatty alcohol and transition metal (iron powder) was 1: 0.12; When transition metal was brown iron oxide, the molar mass ratio of natural fatty alcohol and transition metal (brown iron oxide) was 1: 0.17.
The invention has the beneficial effects as follows: viscosity-depression agent of the present invention is take natural fatty alcohol as raw material, and raw material is easy to get, and preparation technology is simple; The contained manthanoate group of viscosity-depression agent has certain hydrogen supply capacity (carbonyl hydrogen relatively active, be easy to dissociate), the contained amphiphilic group of viscosity-depression agent can impel it with crude oil, to contact more fully, can farthest bring into play the catalytic activity of transition metal, thereby can at the temperature of 200 ℃, impel special super viscous crude generation part catalytic pyrolysis, hydrogenation reaction, change simultaneously the viscous crude molecular structure, the irreversible reduction viscosity of thickened oil of part, improve the quality of viscous crude to a certain extent.The indoor application evaluation shows, at 200 ℃, consumption, is under the condition of 0.2～0.3wt%, and this viscosity-depression agent can reach more than 85% the viscosity break ratio of viscosity less than the spy of 100000mPaS, super viscous crude, has good viscosity reducing effect and universality.
Ester bond in viscosity-depression agent of the present invention is easy to biological degradation, little to the environment negative impact, belong to the environmental type heavy crude thinner, and the characteristics such as have raw material abundance, moderate cost, preparation technology is simple, site operation is convenient and safe, be applicable to site technique condition and the technology of present viscous oil recovery, therefore aspect viscous crude (particularly special super viscous crude) hydrothermal cracking and catalyzing cracking viscosity reduction exploitation, good practical value and wide market outlook arranged.
Embodiment
For a better understanding of the present invention, below in conjunction with embodiment, further illustrate content of the present invention, but content of the present invention not only is confined to the following examples (only be accurate to radix point after 2 figure places).In the embodiment of the present invention, related viscosity is that the DV-II+ type programmable control standard viscometer that adopts U.S. Briekfield company to produce records.
Embodiment 1:
The preparation method of the alkyl ester sulfonate complex compound viscosity-depression agent of tool hydrogen supply structure, it comprises the steps: 1.0mol lauryl alcohol (C12) and 5.0mol formic acid are added in there-necked flask, at 70 ℃, carry out esterification 1.0h, with the 2.0mol ethylene dichloride, dissolve again, be positioned in ice-water bath, stir, at the uniform velocity drip 1.3mol chlorsulfonic acid sulfonation reaction 0.5h, after sulfonation completes, be warming up to 70 ℃ of aging 1.0h, obtain intermediate product; Then the 0.12mol iron powder is added in above-mentioned reaction system (intermediate product), under 100 ℃, carry out complex reaction 1.0h, standing, layering after reaction finishes, remove the water on upper strata, under 60 ℃, after drying, lower floor's wax is the alkyl ester sulfonate complex compound viscosity-depression agent (product) of tool hydrogen supply structure.Industrial production can be amplified and get final product in proportion with industrial raw material.
The alkyl ester sulfonate complex compound viscosity-depression agent of resulting tool hydrogen supply structure, its chemical name are the alkyl ester sulfonic acid iron complex of tool hydrogen supply structure, and wherein alkyl ester is by lauryl alcohol and formic acid, to carry out esterification to make, and transition metal used is iron powder.
Application:
By the special viscous crude (50 ℃ lower viscosity be 48000mPaS) of the present embodiment product application in the Shandong Shengli Oil Field, this viscosity-depression agent (the present embodiment product), water and special viscous crude are placed in to autoclave, under 200 ℃, carry out the hydrothermal cracking and catalyzing scission reaction, wherein take whole system quality as benchmark, the viscosity-depression agent consumption is 0.3wt% (mass percent), and amount of water is 40wt% (mass percent); After reaction, the reducing thick oil viscosity rate reaches 86.7%, and has 9.4% heavy component to be cracked into light component.Illustrate that the present invention is respond well at 200 ℃ of lower viscosity reductions.
Embodiment 2:
The preparation method of the alkyl ester sulfonate complex compound viscosity-depression agent of tool hydrogen supply structure, it comprises the steps: 1.0mol tetradecyl alcohol (C14) and 6.0mol formic acid are added in there-necked flask, at 80 ℃, carry out esterification 1.5h, with the 2.2mol ethylene dichloride, dissolve again, be positioned in ice-water bath, stir, at the uniform velocity drip 1.5mol chlorsulfonic acid sulfonation reaction 0.7h, after sulfonation completes, be warming up to 80 ℃ of aging 1.3h; Then the 0.12mol iron powder is added in above-mentioned reaction system, under 110 ℃, carry out complex reaction 1.3h, standing, layering after reaction finishes, remove the water on upper strata, under 60 ℃, after drying, lower floor's wax is the alkyl ester sulfonate complex compound viscosity-depression agent (product) of tool hydrogen supply structure.Industrial production can be amplified and get final product in proportion with industrial raw material.
The alkyl ester sulfonate complex compound viscosity-depression agent of resulting tool hydrogen supply structure, its chemical name are the alkyl ester sulfonic acid iron complex of tool hydrogen supply structure, and wherein alkyl ester is by tetradecyl alcohol and formic acid, to carry out esterification to make, and transition metal used is iron powder.
Application:
By the super viscous crude (50 ℃ lower viscosity be 81000mPaS) of the present embodiment product application in Karamay Oil Fields in Xinjiang, this viscosity-depression agent (the present embodiment product), water and super viscous crude are placed in to autoclave, under 200 ℃, carry out the hydrothermal cracking and catalyzing scission reaction, wherein take whole system quality as benchmark, the viscosity-depression agent consumption is 0.2wt% (mass percent), and amount of water is 25wt% (mass percent); After reaction, the reducing thick oil viscosity rate reaches 96.3%, and has 12.7% heavy component to be cracked into light component.Illustrate that the present invention is respond well at 200 ℃ of lower viscosity reductions.
Embodiment 3:
The preparation method of the alkyl ester sulfonate complex compound viscosity-depression agent of tool hydrogen supply structure, it comprises the steps: 1.0mol palmityl alcohol (C16) and 7.0mol formic acid are added in there-necked flask, at 80 ℃, carry out esterification 2.0h, with the 2.4mol ethylene dichloride, dissolve again, be positioned in ice-water bath, stir, at the uniform velocity drip 1.7mol chlorsulfonic acid sulfonation reaction 0.8h, after sulfonation completes, be warming up to 80 ℃ of aging 1.6h; Then the 0.12mol iron powder is added in above-mentioned reaction system, under 120 ℃, carry out complex reaction 1.6h, standing, layering after reaction finishes, remove the water on upper strata, under 60 ℃, after drying, lower floor's wax is the alkyl ester sulfonate complex compound viscosity-depression agent (product) of tool hydrogen supply structure.Industrial production can be amplified and get final product in proportion with industrial raw material.
The alkyl ester sulfonate complex compound viscosity-depression agent of resulting tool hydrogen supply structure, its chemical name are the alkyl ester sulfonic acid iron complex of tool hydrogen supply structure, and wherein alkyl ester is by palmityl alcohol and formic acid, to carry out esterification to make, and transition metal used is iron powder.
Application:
By the super viscous crude (50 ℃ lower viscosity be 95000mPaS) of the present embodiment product application in the Shandong Shengli Oil Field, this viscosity-depression agent (the present embodiment product), water and viscous crude are placed in to autoclave, under 200 ℃, carry out the hydrothermal cracking and catalyzing scission reaction, wherein take whole system quality as benchmark, the viscosity-depression agent consumption is 0.3wt% (mass percent), and amount of water is 30wt% (mass percent); After reaction, the reducing thick oil viscosity rate reaches 87.5%, and has 10.3% heavy component to be cracked into light component.Illustrate that the present invention is respond well at 200 ℃ of lower viscosity reductions.
Embodiment 4:
The preparation method of the alkyl ester sulfonate complex compound viscosity-depression agent of tool hydrogen supply structure, it comprises the steps: 1.0mol stearyl alcohol (C18) and 8.0mol formic acid are added in there-necked flask, at 90 ℃, carry out esterification 2.0h, with the 2.5mol ethylene dichloride, dissolve again, be positioned in ice-water bath, stir, at the uniform velocity drip 1.8mol chlorsulfonic acid sulfonation reaction 1.0h, after sulfonation completes, be warming up to 90 ℃ of aging 2.0h; Then the 0.12mol iron powder is added in above-mentioned reaction system, carry out complex reaction 2.0h under 120 ℃, standing, layering after reaction finishes, remove the water on upper strata, and after drying, lower floor's wax is the alkyl ester sulfonate complex compound viscosity-depression agent of tool hydrogen supply structure under 60 ℃.Industrial production can be amplified and get final product in proportion with industrial raw material.
The alkyl ester sulfonate complex compound viscosity-depression agent of resulting tool hydrogen supply structure, its chemical name are the alkyl ester sulfonic acid iron complex of tool hydrogen supply structure, and wherein alkyl ester is by stearyl alcohol and formic acid, to carry out esterification to make, and transition metal used is iron powder.
Application:
The present embodiment product (the alkyl ester sulfonate complex compound viscosity-depression agent of tool hydrogen supply structure) is applied to the super viscous crude (50 ℃ of lower viscosity are 60500mPaS) of Karamay Oil Fields in Xinjiang, this viscosity-depression agent (the present embodiment product), water and viscous crude are placed in to autoclave, under 200 ℃, carry out the hydrothermal cracking and catalyzing scission reaction, wherein take whole system quality as benchmark, the viscosity-depression agent consumption is 0.2wt% (mass percent), and amount of water is 35wt% (mass percent); After reaction, the reducing thick oil viscosity rate reaches 93.9%, and has 11.8% heavy component to be cracked into light component.Illustrate that the present invention is respond well at 200 ℃ of lower viscosity reductions.
Embodiment 5:
With embodiment 1 or 2 or 3 or 4 basic identical, difference is: with the 0.17mol brown iron oxide, replace 0.12mol iron powder, the alkyl ester sulfonate complex compound viscosity-depression agent of resulting tool hydrogen supply structure.Under same application, after reaction, the reducing thick oil viscosity rate all reaches more than 85%, illustrates that the present invention is better at 200 ℃ of lower viscosity reducing effects.
Embodiment 6:
With embodiment 1 or 2 or 3 or 4 basic identical, difference is: 0.3mol tetradecyl alcohol (C14), 0.3mol palmityl alcohol (C16) and 0.4mol stearyl alcohol (C18) are replaced 1.0mol lauryl alcohol (C12).Under same application, after reaction, the reducing thick oil viscosity rate all reaches more than 85%, illustrates that the present invention is better at 200 ℃ of lower viscosity reducing effects.
Bound value, the interval value of each raw material that the present invention is cited can be realized the present invention, and bound value and the interval value of processing parameter of the present invention (as temperature, time rate etc.) can be realized the present invention, at this, do not enumerate embodiment.
Claims (3)
1. have an alkyl ester sulfonate complex compound reducing viscosity in hydrothermal cracking and catalyzing thick oil agent of hydrogen supply structure, the chemical name that it is characterized in that it is the alkyl ester sulfonic acid iron complex of tool hydrogen supply structure;
Described alkyl ester is by the natural fatty alcohol of C12～C18 and formic acid, to carry out esterification to make;
Described iron complex is to be made by brown iron oxide or iron powder generation complex reaction.
2. a method for preparing the alkyl ester sulfonate complex compound reducing viscosity in hydrothermal cracking and catalyzing thick oil agent of tool hydrogen supply structure claimed in claim 1, is characterized in that it comprises the steps:
1) mol ratio by natural fatty alcohol and formic acid is 1:5.0～8.0, chooses natural fatty alcohol and formic acid, joins in container, is heated to 70～90 ℃ and carries out esterification 1～2 h, obtains alkyl ester;
2) mol ratio by natural fatty alcohol and ethylene dichloride is 1:2.0～2.5, chooses ethylene dichloride, joins in described container;
3) described container is positioned in ice-water bath, mol ratio by natural fatty alcohol and chlorsulfonic acid is 1:1.3～1.8, choose chlorsulfonic acid, to at the uniform velocity dripping chlorsulfonic acid in container, carry out sulfonation reaction, sulfonation 0.5～1 h, after sulfonation completes, be warming up to 70～90 ℃ of aging 1～2 h, obtain intermediate product;
4) mol ratio by natural fatty alcohol and transition metal material is 1:0.12 or 1:0.17, chooses transition metal material,
Described transition metal material is any one in iron powder, brown iron oxide; When transition metal material was iron powder, the mol ratio of natural fatty alcohol and transition metal material was 1:0.12; When transition metal material was brown iron oxide, the mol ratio of natural fatty alcohol and transition metal material was 1:0.17;
In at 100～120 ℃, transition metal material being joined to intermediate product, carry out complex reaction, reaction 1～2 h; Stratification after reaction finishes, remove the water on upper strata, and after drying, lower floor's wax is the alkyl ester sulfonate complex compound reducing viscosity in hydrothermal cracking and catalyzing thick oil agent of tool hydrogen supply structure under 60 ℃.
3. the preparation method of the alkyl ester sulfonate complex compound reducing viscosity in hydrothermal cracking and catalyzing thick oil agent of tool hydrogen supply structure according to claim 2, it is characterized in that: described natural fatty alcohol is one or two or more kinds mixture by any proportioning in lauryl alcohol, tetradecyl alcohol, palmityl alcohol, stearyl alcohol.
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| CN103937467B (en) * | 2013-01-21 | 2016-08-03 | 中国石油化工股份有限公司 | Thick oil hydrothermal catalytic thinner and preparation method thereof and transient metal complex and part |
| CN104650835A (en) * | 2013-11-20 | 2015-05-27 | 新疆贝肯石油科技开发有限责任公司 | Fluidized bed fly ash adjustment agent |
| CN104695918B (en) * | 2013-12-04 | 2018-06-08 | 中国石油化工股份有限公司 | A kind of viscous crude underground modifies viscosity-reduction oil-extraction method |
| CN106543998B (en) * | 2016-10-19 | 2020-06-12 | 中国石油化工股份有限公司 | Hydrothermal cracking catalytic viscosity reducer and preparation method thereof |
| CN106622363B (en) * | 2016-11-23 | 2020-04-24 | 长江大学 | Catalytic viscosity reducer composition, catalytic viscosity reducer and application of catalytic viscosity reducer |
| CN113388125B (en) * | 2021-05-27 | 2022-07-12 | 长江大学 | Copper-based metal organic framework material, thickened oil viscosity reducer and preparation method thereof |
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| CN1272393A (en) * | 1999-04-30 | 2000-11-08 | 大庆石油管理局 | Alkyl benzene sulfonate surfactant, its preparation method and application in tertiary oil recovery |
| CN102154000A (en) * | 2011-02-11 | 2011-08-17 | 中国地质大学（武汉） | Transition metal sulfonate complex thick oil water thermo-catalysis viscosity reducer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1272393A (en) * | 1999-04-30 | 2000-11-08 | 大庆石油管理局 | Alkyl benzene sulfonate surfactant, its preparation method and application in tertiary oil recovery |
| CN102154000A (en) * | 2011-02-11 | 2011-08-17 | 中国地质大学（武汉） | Transition metal sulfonate complex thick oil water thermo-catalysis viscosity reducer and preparation method thereof |
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