CN102140909A - Method for reducing viscosity of heavy oil by emulsification - Google Patents
Method for reducing viscosity of heavy oil by emulsification Download PDFInfo
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Abstract
The invention relates to a method for reducing the viscosity of heavy oil by emulsification. The method comprises the following steps: mixing an agent A selected from one or more of distillate oil, light oil or medium oil from a refinery plant, with the heavy oil; adding an agent B into the mixture of the heavy oil and the agent A; and blending to form an oil-in-water emulsion, wherein the agent B consists of an anionic surfactant, a nonionic-anionic surfactant and water. The method obviates the use of alkali and has high mineral salt tolerance. Particularly, the method can be used for emulsifying heavy oil with the ultra-high viscosity of 500,000mPa.s at 50 DEG C at moderate cost, and the emulsified heavy oil has low viscosity.
Description
Technical field
The present invention relates to a kind of method of thick-oil emulsified adhesive-reducing.
Background technology
In recent years, International Crude Oil continues in high position vibration, and oil demand is constantly soaring, and thought does not have the marginal heavy oil of extraction value and pitch reservoir in the past, becomes the efficient resource of economically valuable.Contain more colloid and asphalitine in the viscous crude, viscosity is big, and mobile poor, the exploitation difficulty is big, and recovery ratio is lower.The reducing viscosity by emulsifying method is a present heavy crude producing method commonly used, in the heavy oil block successful Application on ground such as China's Shengli Oil Field, Liaohe Oil Field.Emulsifier and mineralized water are mixed, add from oil well casing then, mix with the viscous crude from the stratum filtration to the pit shaft, emulsifier reduces oil water interfacial tension greatly, formation is decentralized photo with the viscous crude, water is the O/W type emulsion system of continuous phase, has stoped the gathering of oil droplet, thereby reduces viscosity of thickened oil.Because the viscosity of continuous phase water is very low, friction becomes the friction between water and tube wall in the viscous crude, greatly reduces the flow resistance in the pit shaft, and fluid viscosity significantly reduces, and wellhead back pressure power also significantly reduces, and power consumption reduces, thereby increases substantially tar productivity.
Along with the increase of the thickened oil recovery degree of depth, geological conditions is complicated day by day, and the reserves of special viscous crude and super viscous crude continue to increase, and the salinity of formation water also constantly increases.The oil reservoir that oil fields such as the Tahe of China, Tarim Basin have been found, formation water salinity is up to 200000mg/L, and there are the colloid of quite a few viscous crude, asphalt content very high, 50 ℃ of viscosity of viscous crude are greater than 500,000mPa.s, asphalitine forms very strong adsorbed film at oil-water interfaces, and the interface film strength is very high, replaces and makes viscous oil emulsion generation phase inversion reduce viscosity thereby the reducing viscosity by emulsifying agent molecule is difficult in oil-water interfaces.According to the The field situation, less than 500, the emulsification of crude oil viscosity reducing effect of 000mPa.S is better for 50 ℃ of viscosity for the reducing viscosity by emulsifying method, but for 50 ℃ of viscosity greater than 500,000mPa.S even up to 1,000, the viscous crude of 000mPa.S is inapplicable substantially.
At present, in the emulsifying pour depressor that the oil field is used always, the more emulsifier of bibliographical information and practical application is non-ionic surface active agent, anionic surfactant, and there is following shortcoming in they, for example:
CN 88105018A has reported with polyoxyethylated alkyl phenol and the composite method as thick oil emulsifier of alkali.In addition, other patent has also been reported with the method for non-ionic surface active agents such as polyxyethylated alcohol, polyoxyethylene sorbitan esters, polyoxyethylene oxypropylene polyethylene polyamine, polyoxyethylene oxypropylene propylene glycol as thick oil emulsifier.The cost of production of above-mentioned nonionic surface active agent is higher, the ability of anti-rock salt is generally less than 1000mg/L, under higher salinity, and obvious variation of reducing viscosity by emulsifying effect even inefficacy, greater than 500, the viscous crude of 000mPa.S is powerless especially for 50 ℃ of viscosity.
US 5934303 has reported the method for a kind of sodium salt, magnesium salts or ammonium salt with naphthalene sulfonic acid-formaldehyde condensation product as emulsifying and viscosity-reducing agent for condensed oil, is suitable in total ion concentration is the formation water of 38000mg/L (calcium magnesium is 6200mg/L).US 4016932 has reported that with the composite method as oil displacement agent of the petroleum sulfonate of not condensation, NPE and alkali can be used for total ion concentration is 125000mg/L (Ca
2+, Mg
2+Be 5800mg/L) formation water.But be not suitable for heavy crude producing and super viscous crude.Because contain a large amount of asphalitines and colloid in the viscous crude, mining conditions is more special.And for the calcium magnesium density in the formation water during greater than 10000mg/L, also ineffective.
CN 1340589A has reported a kind of APEO type non-ionic surface active agent and the aromatic acid of replacement and condensation product of aromatic sulfonic acid anion surfactant of aryl end socket, in the presence of alkali, be applicable to the reducing viscosity by emulsifying of the viscous crude that asphalitine and gum level are high, but it is, then ineffective when the calcium magnesium density in the formation water during greater than 2000mg/L.
US 2007/0042911 has reported a kind of emulsifying and viscosity-reducing agent for condensed oil, with the polyvinyl alcohol is the commissure polymer that skeleton obtains, adding dosage is under 0.5% the condition viscosity of common heavy oil is dropped to about 200mPa.s, also is not suitable for the viscosity reduction of super viscous crude, loses the viscosity reduction effect especially under the high salinity condition.
In the system in Tahe Oilfield in China Zhongyuan Oil Field and Xinjiang, tell and breathe out oil field etc., the calcium ions and magnesium ions concentration of formation water is sometimes greater than 10000mg/L.CN100363456C has reported the emulsifying and viscosity-reducing agent for condensed oil that is used under this type of high salinity condition, is the compound of anion surfactant and nonionic-anion surfactant, demulsifier.Though have very high anti-salt property, for the super viscous crude of 50 ℃ of viscosity greater than 500000mPa.s, the reducing viscosity by emulsifying method is still inapplicable.
Summary of the invention
The technical problem that will solve of the present invention provides a kind of method of thick-oil emulsified adhesive-reducing, and this method does not use alkali, anti-rock salt ability strong, can 50 ℃ of viscosity of emulsification greater than 500,000mPa.s superelevation viscous crude, and the viscosity of thickened oil after the emulsification is low.
Method provided by the invention comprises:
(1) the A agent is mixed with viscous crude, the weight ratio of A agent and viscous crude is 0.05-1: 1, and described A agent is selected from one or more in refinery's distillate, light oil or the middle matter oil;
(2) the B agent is joined in the mixture of viscous crude and A agent, mix the back and form oil-in-water emulsion, with viscous crude weight is benchmark, B agent consumption is 500-20000 μ g/g, described B agent is made up of anion surfactant, nonionic-anion surfactant and water, the mass fraction of surfactant in the B agent is 1-50000 μ g/g, and the mass ratio of anion surfactant and nonionic-anion surfactant is 1: 0.1-0.1: 1.
The weight ratio of A agent and viscous crude is preferably 0.05-0.2: 1.
Described distillate can be selected from oil refinery one or more once or in the naphtha that obtains of secondary operations, gasoline, kerosene, diesel oil, is preferably naphtha.
Density≤the 0.87g/cm of described light oil
3, the density＞0.87g/cm of middle matter oil
3And≤0.92g/cm
3Generally speaking, 50 ℃ of viscosity≤2000mPa.s of light oil or middle matter oil.Among the present invention, described A agent is preferably the light oil of 50 ℃ of viscosity≤100mPa.s.
In the step (2), B agent consumption is preferably 1000-10000 μ g/g.
The mass fraction of surfactant in the B agent is preferably 100-20000 μ g/g.The mass ratio of anion surfactant and nonionic-anion surfactant is preferably 1: 0.2-0.5: 1.
Described anion surfactant is preferably the sodium salt and/or the calcium salt of petroleum sulfonate formaldehyde condensation products, and molecular weight is 500-40000, is preferably 1000-20000; Perhaps alkylaryl sulfonates, lignosulfonates, heavy alkylbenzene sulfonate etc.Can be the commercial goods, also can prepare according to conventional method.
Described nonionic-anionic surfactant is selected from one or more in phosphate ester salt, sulfuric acid, carboxylate and the sulfonate of APEO or polyoxyethylene poly-oxygen propylene aether.
The initiator of APEO or polyoxyethylene poly-oxygen propylene aether is alkyl phenol, polyethylene polyamine or fatty alcohol.
When being initiator with alkyl phenol or fatty alcohol, the general formula of nonionic-anionic surfactant is written as respectively:
R-O-(CH
2CH
2O)
n-[CH
2CH(CH
3)O]
mPO
3M
2
R-O-(CH
2CH
2O)
n-[CH
2CH(CH
3)O]
mSO
3M
R-O-(CH
2CH
2O)
n-[CH
2CH(CH
3)O]
mCH
2COOM
R-O-(CH
2CH
2O)
n-[CH
2CH(CH
3)O]mR’SO
3M
R is alkyl or alkane phenyl, and total carbon number is 6-20, preferred 8-18; N is an oxygen vinyl polymerization degree, and its value is 3-90; M is monovalence metal cation or NH
4 +, the carbon number of R ' is the 1-6 scope.M is the oxypropylene degree of polymerization, and its value is 0-90.Preferred nonionic-anionic surfactant is: C6-C20 alkyl phenol (or fatty alcohol) polyoxyethylene poly-oxygen propylene aether carboxylate, C6-C20 alkyl phenol (or fatty alcohol) polyoxyethylene poly-oxygen propylene aether sulfonate, C6-C20 alkyl phenol (or fatty alcohol) polyoxyethylene poly-oxygen propylene aether phosphate ester salt, C6-C20 alkyl phenol (or fatty alcohol) polyoxyethylene poly-oxygen propylene aether sulfuric acid.
Described water can be common water quality, as tap water, well water, distilled water, also can be the formation water that total salinity is not more than 200000mg/L.
Method of the present invention can be used for the reducing viscosity by emulsifying of viscous crude, is specially adapted to the reducing viscosity by emulsifying of super viscous crude.
Main innovate point of the present invention is the method that adopts thin oil blending visbreaking and water-emulsifiable viscosity reduction to use simultaneously, can significantly reduce the viscosity of super viscous crude.Super viscous crude has very high asphalt content usually, and asphalitine forms very stable lamellar structure by hydrogen bond action, makes crude oil have big viscosity.The distillate or light oil or the middle matter oil that in producing well, add oil refinery, asphalitine is separated form, disperse, form colloidal solution uniform, that viscosity reduces relatively, less at this colloidal solution medium pitch matter particle, do the time spent with the water-emulsifiable thinner, the oil-in-water type water-oil emulsion that easier formation is stable.
Compared with prior art, reducing viscosity by emulsifying method of the present invention is not used alkali, and anti-rock salt ability is strong, particularly can 50 ℃ of viscosity of emulsification greater than 500, the hyperviscosity viscous crude of 000mPa.s, and the viscosity of thickened oil after the emulsification is low, the emulsification cost is moderate.
The specific embodiment
A agent and B agent can prepare and use in accordance with the following methods: earlier the A agent is added in the viscous crude, mix, then surfactant and water are mixed, be made into the B agent.Again the B agent is added in viscous crude and the A agent composition, mix the back and form even oil-in-water emulsion.
Example 1
Take by weighing the 1g naphtha as the A agent, with itself and 50 ℃ of viscosity of 10g is 1,080,000mPa.s Xinjiang Tahe high viscous crude mix, take by weighing 0.08g octyl phenol polyoxy ethene polyethenoxy ether sulphonic acid ester then, 0.01g petroleum sodium sulfonate formaldehyde condensation products is dissolved in the formation water that the 4.24g total salinity is 45000mg/L, is made into the B agent aqueous solution.The B agent aqueous solution is joined in the miscella of above-mentioned A agent and viscous crude, 60 ℃ are stirred formation stabilised oil-in-water emulsion after 2 minutes down, measure emulsion viscosity, the results are shown in Table 1 again.
Example 2
Take by weighing 10g kerosene as the A agent, with itself and 50 ℃ of viscosity of 10g is 1,800,000mPa.s Xinjiang Tahe high viscous crude mix, taking by weighing 0.06g lauryl alcohol polyoxyethylene poly-oxygen propylene aether carboxylate, 0.04g calcium mahogany sulfonate formaldehyde condensation products then, to be dissolved in the 8.57g total salinity be 200, the formation water of 000mg/L is made into the B agent aqueous solution.The B agent aqueous solution is joined in the miscella of above-mentioned A agent and viscous crude, 60 ℃ are stirred formation stabilised oil-in-water emulsion after 2 minutes down, measure emulsion viscosity, the results are shown in Table 1 again.
Comparative Examples 1
Press example 1 described method preparation B agent, wherein octyl phenol polyoxy ethene polyethenoxy ether sulphonic acid ester increases to 0.1g.Is 1,080 with the B agent by example 1 described method and 50 ℃ of viscosity, and the Xinjiang Tahe high viscous crude of 000mPa.s mixed 5 minutes, did not form the stabilize oil aqueous emulsion.
Comparative Examples 2
Press example 2 described method preparation B agent, wherein lauryl alcohol polyoxyethylene poly-oxygen propylene aether carboxylate increases to 0.2g.Is 1,080 with the B agent by example 2 described methods and 50 ℃ of viscosity, and the Xinjiang high viscous crude of 000mPa.s mixed 5 minutes, did not form the stabilize oil aqueous emulsion.
Table 1
Claims (14)
1. ten thousand methods of a thick-oil emulsified adhesive-reducing comprise:
(1) the A agent is mixed with viscous crude, the weight ratio of A agent and viscous crude is 0.05-1: 1, and described A agent is selected from one or more in refinery's distillate, light oil or the middle matter oil;
(2) the B agent is joined in the mixture of viscous crude and A agent, mix the back and form oil-in-water emulsion, with viscous crude weight is benchmark, B agent consumption is 500-20000 μ g/g, described B agent is made up of anion surfactant, nonionic-anion surfactant and water, the mass fraction of surfactant in the B agent is 1-50000 μ g/g, and the mass ratio of anion surfactant and nonionic-anion surfactant is 1: 0.1-0.1: 1.
2. in accordance with the method for claim 1, it is characterized in that the weight ratio of A agent and viscous crude is 0.05-0.2.
3. in accordance with the method for claim 1, it is characterized in that, is benchmark with the viscous crude, and B agent consumption is 1000-10000 μ g/g.
4. in accordance with the method for claim 1, it is characterized in that described distillate is selected from oil refinery one or more once or in the naphtha that obtains of secondary operations, gasoline, kerosene, diesel oil.
5. in accordance with the method for claim 1, it is characterized in that 50 ℃ of viscosity of described light oil or middle matter oil are less than 100mPa.s.
6. in accordance with the method for claim 1, it is characterized in that the mass fraction of surfactant in the B agent is 100-20000 μ g/g.
7. in accordance with the method for claim 1, it is characterized in that the mass ratio of anion surfactant and nonionic-anion surfactant is 1: 0.2-0.5: 1.
8. in accordance with the method for claim 1, it is characterized in that described anion surfactant is the sodium salt and/or the calcium salt of petroleum sulfonate formaldehyde condensation products, molecular weight is 500-40000.
9. in accordance with the method for claim 8, it is characterized in that the sodium salt of described petroleum sulfonate formaldehyde condensation products and/or the molecular weight of calcium salt are 1000-20000.
10. in accordance with the method for claim 1, it is characterized in that described nonionic-anionic surfactant is selected from one or more in phosphate ester salt, sulfuric acid, carboxylate and the sulfonate of APEO or polyoxyethylene poly-oxygen propylene aether.
11. in accordance with the method for claim 10, it is characterized in that the degree of polymerization of oxygen ethene is 3-90.
12. in accordance with the method for claim 10, it is characterized in that the initiator of APEO or polyoxyethylene poly-oxygen propylene aether is alkyl phenol, polyethylene polyamine or fatty alcohol.
13. in accordance with the method for claim 12, it is characterized in that the alkyl carbon number of alkyl phenol or fatty alcohol is 6-20.
14. oil-in-water emulsion according to the arbitrary method preparation of claim 1-13.
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| CN103114835A (en) * | 2013-03-18 | 2013-05-22 | 西南石油大学 | Nitrogen-aided thickened oil formation emulsification and viscosity reduction exploitation method |
| CN103540304A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Surfactant composition for intensified oil production and preparation method thereof |
| CN103666411A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Compound oil base emulsifier containing fatty alcohol polyoxyethylene polypropylene ether sulfonate and preparation method of compound oil base emulsifier |
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| CN116179177A (en) * | 2023-04-23 | 2023-05-30 | 西南石油大学 | Preparation method of compound surfactant thickened oil microemulsion |
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Application publication date: 20110803 |