CN103361108B - A kind of emulsion splitter being applicable to high-sulfur height salt Produced Liquid crude oil emulsion - Google Patents
A kind of emulsion splitter being applicable to high-sulfur height salt Produced Liquid crude oil emulsion Download PDFInfo
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- CN103361108B CN103361108B CN201310247125.XA CN201310247125A CN103361108B CN 103361108 B CN103361108 B CN 103361108B CN 201310247125 A CN201310247125 A CN 201310247125A CN 103361108 B CN103361108 B CN 103361108B
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- crude oil
- produced liquid
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- sulfur
- salt produced
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- 239000010779 crude oil Substances 0.000 title claims abstract description 26
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 22
- 239000011593 sulfur Substances 0.000 title claims abstract description 22
- 239000000839 emulsion Substances 0.000 title claims abstract description 17
- 239000007788 liquid Substances 0.000 title claims abstract description 14
- 150000003839 salts Chemical class 0.000 title abstract description 12
- 239000002798 polar solvent Substances 0.000 claims abstract description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
- 229920013639 polyalphaolefin Polymers 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 8
- 238000011160 research Methods 0.000 abstract description 2
- 229920006163 vinyl copolymer Polymers 0.000 abstract 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 9
- 230000018044 dehydration Effects 0.000 description 9
- 238000006297 dehydration reaction Methods 0.000 description 9
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 8
- 239000012530 fluid Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000004711 α-olefin Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- -1 polysiloxane Polymers 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 108010011935 Poly 18 antigen Proteins 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a kind of emulsion splitter being applicable to high-sulfur height salt Produced Liquid crude oil emulsion, comprise the raw material of following weight percent: 60% ~ 65% silicon-containing surfactant, the vinyl copolymer of 1% ~ 5%, the polar solvent of 25% ~ 30%.Namely the present invention is compositing characteristic for such Produced Liquid and researches and develops, it effectively can improve breaking emulsion and dewatering efficiency, reduce dosing, guarantee de-after crude oil water containing to conform with the regulations requirement, and effectively can reduce the energy expenditure in treating processes.Namely when dosage reduces by 20%, dewatering efficiency improves more than 30%, de-rear crude oil water containing can be down to less than 0.2%.
Description
Technical Field
The invention relates to a demulsifier suitable for a high-sulfur high-salt produced liquid crude oil emulsion.
Background
Various demulsifiers for oilfield produced fluids are available. In terms of structure type, different initiators are mainly connected with polyethylene oxide and propylene oxide; from the aspect of molecular conformation, the molecular conformation mainly comprises straight chains, multiple branched chains, star shapes and tree shapes; from the application range, the oil-water separator is universal, low-temperature, water-purifying and specific to special oil types.
The high-sulfur high-salt produced liquid is a kind of produced liquid with special composition and property, and a proper demulsifier structure must be determined according to the characteristics of the produced liquid to obtain a good effect. At present, some demulsifiers aiming at high-sulfur and high-salt produced fluids exist, but due to market demands, the upper limits of sulfur and salt contents of the produced fluids suitable for the existing demulsifiers are lower, and research on the demulsifiers aiming at the produced fluids with the characteristics of high sulfur and high salt is still in the process of starting.
The existing demulsifier is applied to demulsification and dehydration of high-sulfur high-salt produced fluid, and still has the problems of high usage amount, high energy consumption, unstable water content index of treated crude oil and the like.
Disclosure of Invention
The invention aims to solve the technical problem of providing a demulsifier suitable for demulsification and dehydration of produced fluid of an oil field, in particular to a demulsifier for demulsification and dehydration of produced fluid with the characteristics of high sulfur and high salt composition. When the dosage of the demulsifier for the high-sulfur high-salt crude oil emulsion is less than 150mg/L, the demulsifier can achieve the target that the water content of the crude oil after dehydration is less than 0.2 percent
The technical scheme for solving the technical problems is as follows: the demulsifier suitable for the crude oil emulsion of the high-sulfur high-salt produced liquid comprises the following raw materials in percentage by weight: 60 to 65 percent of silicon-containing surfactant, 1 to 5 percent of alkene copolymer and 25 to 30 percent of polar solvent; wherein,
the molecular structure of the silicon-containing surfactant is as follows:
r is 3-30; m is 1-60; n is 1-60; r1Is a C1-C9 hydrocarbon group;
the alkene copolymer is poly alpha-olefin, and the carbon number of an alkyl side chain is 10-20;
the polar solvent is polyhydric alcohol, and the carbon number is 2-5.
With the improvement of crude oil extraction technology and the continuous increase of energy demand, the yield of a large amount of crude oil with complex composition and poor quality is higher and higher. Among them is high sulfur and high salt crude oil. The composition of the method is characterized by high sulfur content and high salt content in produced liquid. Chemical substances such as sulfur, salt and the like can increase the stability of the produced emulsion and make demulsification and dehydration difficult through a series of physical and chemical actions. Not only greatly increases the energy consumption in the gathering and transportation process, but also causes the water content of the ore removal crude oil to be incapable of meeting the specified index requirement, so that the oil field production cannot be normally carried out.
The invention has the beneficial effects that: the invention is developed aiming at the composition characteristics of the produced liquid, can effectively improve the demulsification and dehydration efficiency, reduce the dosage of the medicament, ensure that the water content of the dehydrated crude oil meets the specified requirements, and can effectively reduce the energy consumption in the treatment process. Namely, under the condition that the dosage is reduced by 20 percent, the dehydration efficiency is improved by more than 30 percent, and the water content of the crude oil after dehydration can be reduced to less than 0.2 percent.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, the polar solvent is any one of dihydric alcohol or trihydric alcohol.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
The demulsifier suitable for the crude oil emulsion of the high-sulfur high-salt produced liquid comprises the following raw materials in percentage by weight: 60 to 65 percent of silicon-containing surfactant, 1 to 5 percent of alkene copolymer and 25 to 30 percent of polar solvent; wherein,
the molecular structure of the silicon-containing surfactant is as follows:
r is 3-30; m is 1-60; n is 1-60; r1Is a C1-C9 hydrocarbon group;
the alkene copolymer is poly alpha-olefin, and the carbon number of an alkyl side chain is 10-20;
the polar solvent is polyhydric alcohol, and the carbon number is 2-5. Any one of dihydric alcohols or trihydric alcohols is preferable.
The present invention will be described in detail with reference to the following examples.
Example 1:
putting hydrogen-containing polysiloxane and KOH catalyst into a synthesis kettle, repeatedly filling nitrogen and pumping negative pressure until the oxygen in the kettle is completely converted, slowly heating to 120-150 ℃, dropwise adding PO (propylene oxide) according to a proportion, keeping the pressure at 0.2-0.5 MPa and keeping the temperature at 150 ℃. After the dropwise addition, the temperature was kept constant for 30 min. Then proportionally dripping EO (ethylene oxide), and keeping the pressure at 0.2-0.5 MPa and the temperature not more than 150 ℃. And controlling PO and EO to be 1: 2.5-3. After the dropwise addition, the temperature was kept constant for 40 min. Cooling to below 30 ℃, and sequentially adding poly 12 alkyl alpha-olefin and ethylene glycol to obtain the finished product demulsifier.
The synthesis of poly 12 alkyl alpha olefins is known in the art and will not be described in detail here.
When the demulsifier obtained according to example 1 is used for crude oil emulsion containing 29 ten thousand mg/L of salt and 4% of sulfur, and the dosage is not more than 100mg/L, the water content of the crude oil after being demulsified can be reduced to below 0.2% by using a conventional electric demulsification process.
Example 2:
putting hydrogen-containing polysiloxane and KOH catalyst into a synthesis kettle, repeatedly filling nitrogen and pumping negative pressure until the oxygen in the kettle is completely converted, slowly heating to 120-150 ℃, dropwise adding PO (propylene oxide) according to a proportion, keeping the pressure at 0.2-0.5 MPa and keeping the temperature at 150 ℃. After the dropwise addition, the temperature was kept constant for 30 min. Then proportionally dripping EO (ethylene oxide), and keeping the pressure at 0.2-0.5 MPa and the temperature not more than 150 ℃. EO is 1: 1.5-2. After the dropwise addition, the temperature was kept constant for 40 min. Cooling to below 30 ℃, and sequentially adding poly 18 alkyl alpha-olefin and glycerol to obtain the finished product demulsifier.
The synthesis of poly 18 alkyl alpha olefins is known in the art and will not be described in detail here.
When the demulsifier obtained according to the embodiment 2 is used for crude oil emulsion containing 26 ten thousand mg/L of salt, 3 percent of sulfur and nearly 100000mg/L of chloride ions, and the dosage is not more than 100mg/L, the water content of the crude oil after being dehydrated can be reduced to be less than 0.18 percent by utilizing the conventional electric dehydration process.
Example 3:
putting hydrogen-containing polysiloxane and KOH catalyst into a synthesis kettle, repeatedly filling nitrogen and pumping negative pressure until the oxygen in the kettle is completely converted, slowly heating to 120-150 ℃, dropwise adding PO (propylene oxide) according to a proportion, keeping the pressure at 0.2-0.5 MPa and keeping the temperature at 150 ℃. After the dropwise addition, the temperature was kept constant for 30 min. Then proportionally dripping EO (ethylene oxide), and keeping the pressure at 0.2-0.5 MPa and the temperature not more than 150 ℃. EO is controlled to 1: 3-3.5. After the dropwise addition, the temperature was kept constant for 40 min. Cooling to below 30 ℃, and sequentially adding the mixed polyalkyl alpha-olefin and propylene glycol to obtain the finished product demulsifier.
The synthesis of polyalkyl alpha-olefins is known in the art and is not described in detail here. Wherein the number of carbon atoms in the alkyl group is 12 to 20.
When the demulsifier obtained according to the example 3 is used for crude oil emulsion containing 29 ten thousand mg/L of salt and 4 percent of sulfur, and the dosage of the demulsifier does not exceed 100mg/L, the water content of the crude oil after being demulsified can be reduced to below 0.1 percent by utilizing the conventional electric demulsification process.
The effect of the invention is compared with the conventional demulsifier
Crude oil emulsion properties for testing: salt content 26X 104～30×104mg/L, 3.5-4.5% of sulfur content and 10 multiplied by 10 of chloride ion content4～12×104mg/L, original water content is 4-8%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (2)
1. The demulsifier suitable for the crude oil emulsion of the high-sulfur high-salt produced liquid is characterized by comprising the following raw materials in percentage by weight: 65% of silicon-containing surfactant, 5% of alkene copolymer and 30% of polar solvent; wherein,
the molecular structure of the silicon-containing surfactant is as follows:
r is 3-30; m is 1-60;n＝1～60；R1is a C1-C9 hydrocarbon group;
the alkene copolymer is poly alpha-olefin, and the carbon number of an alkyl side chain is 10-20;
the polar solvent is polyhydric alcohol, and the carbon number is 2-5.
2. The demulsifier for a high-sulfur high-salt produced liquid crude oil emulsion according to claim 1, wherein the polar solvent is any one of dihydric alcohol or trihydric alcohol.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2305124C1 (en) * | 2006-02-22 | 2007-08-27 | Открытое акционерное общество "Татнефть" им. В.Д. Шашина | Composition for dehydration and desalting of crude oil (embodiments) |
| CN101970578A (en) * | 2008-01-25 | 2011-02-09 | 莫门蒂夫性能材料股份有限公司 | Polyorganosiloxane demulsifier compositions and methods of making the same |
| CN102439120A (en) * | 2009-04-03 | 2012-05-02 | 克罗夫化学公司 | Demulsification compositions, systems and methods for demulsifying and separating aqueous emulsions |
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| US7671099B2 (en) * | 2007-08-13 | 2010-03-02 | Rhodia Inc. | Method for spearation crude oil emulsions |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2305124C1 (en) * | 2006-02-22 | 2007-08-27 | Открытое акционерное общество "Татнефть" им. В.Д. Шашина | Composition for dehydration and desalting of crude oil (embodiments) |
| CN101970578A (en) * | 2008-01-25 | 2011-02-09 | 莫门蒂夫性能材料股份有限公司 | Polyorganosiloxane demulsifier compositions and methods of making the same |
| CN102439120A (en) * | 2009-04-03 | 2012-05-02 | 克罗夫化学公司 | Demulsification compositions, systems and methods for demulsifying and separating aqueous emulsions |
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