CN1129469C - Petroleum carboxylate surfactant, its preparation method and application in tertiary oil recovery - Google Patents

Abstract

The present invention relates to a petroleum carboxylate surfactant, the preparation and the application thereof. Petroleum distillate oil is used as raw materials, and petroleum carboxylate is synthetised by oxidation reaction. The present invention has the advantages of wide raw material sources, low preparation price and stable product performance, and can form ultralow interfacial tension with crude oil after an electrolyte is added. The petroleum carboxylate compounding other surfactants has good synergistic effect. A rock core oil displacement test is carried out to a compounding system so that the water ratio is greatly reduced, oil production is concentrated to form a rich oil zone, and the average recovery ratio is enhanced by 20% OOIP than that of water displacement. The surfactant as an oil displacement agent and a compounding agent is applied to tertiary oil recovery and has obvious effect.

Description

Petroleum carboxylate surfactant, its preparation method and the application in tertiary oil recovery thereof

The present invention relates to oil field (displacement of reservoir oil) with surfactant and preparation and application, specifically, for petroleum carboxylate surfactant, its preparation method and as oil displacement agent and the composite dose of application in tertiary oil recovery.

The oil field can enter high water-cut stage through for many years exploitation, and tertiary oil recovery will play an increasingly important role in this class oilfield stable production process.Technique of polymer flooding has entered the industrialization field test stage at present; And the ternary composite driving technology is remarkable in the pilot field test result, dreams of becoming the main tertiary oil recovery method of oilfield stable production.So, use three combination flooding costs higher at present, wherein dosage of surfactant is very big, so, development efficient, cheap oil displacement agent be the ternary composite driving key technology it

Petroleum carboxylate is to be raw material with the fractional oil of crude oil, through the product that the oxidation neutralization obtains, is a kind of anion surfactant of function admirable.Abroad (U.S. University of Pennsylvania) once adopted vapour phase oxidation process synthetic petroleum carboxylate, though conversion ratio is higher relatively, controlled because of difficulty because of process conditions, caused stablizing of properties of product relatively poor.

Purpose of the present invention is to provide tool wide material sources, low interfacial tension, the performance that can be applied in the oil field petroleum carboxylate surfactant efficient, with low cost;

Another object of the present invention, be to provide a kind of easy, practical, easy operating, can obtain with low cost, product stable, the preparation method of above-mentioned petroleum carboxylate surfactant efficiently;

A further object of the present invention is to provide above-mentioned petroleum carboxylate surfactant as the application of oil displacement agent in tertiary oil recovery;

A purpose in addition of the present invention is to provide above-mentioned petroleum carboxylate surfactant as the composite dose of application in tertiary oil recovery.

Technical solution of the present invention comprises:

With the preparation of following method, the petroleum carboxylate surfactant of molecular weight between 380-500, described preparation method may further comprise the steps:

A) select C ₁₀-C ₂₈Between distillate feedstock;

B) oxidation-oxidizing temperature is 100-200 ℃, and the duration is 2-8 hour

The pH value was 8-9 when oxidation was finished;

C) saponification-under 80-120 ℃, with the alkali lye of 20-40%, the mol ratio of alkali and oil carboxylic acid is 1: 1-1: 1.2 transfer to the pH value for 8-9, obtain petroleum carboxylate solution;

D) separation, breakdown of emulsion obtain the product petroleum carboxylate.

Technical solution of the present invention also comprises the preparation method of above-mentioned petroleum carboxylate surfactant, may further comprise the steps:

A) select C ₁₀-C ₂₈Between distillate feedstock;

B) oxidation-oxidizing temperature is 100-200 ℃, and the duration is 2-8 hour

The pH value was 8-9 when oxidation was finished;

C) saponification-under 80-120 ℃, with the alkali lye of 20-40%, the mol ratio of alkali and oil carboxylic acid is 1: 1-1: 1.2 transfer to the pH value for 8-9, obtain petroleum carboxylate solution;

D) separation, breakdown of emulsion obtain the product petroleum carboxylate.

The preparation method of above-mentioned petroleum carboxylate surfactant, the raw material molecular weight is 280-400 in the step a); Be preferably second line of distillation fraction oil.Step b) is preferably under 120 ℃ carries out.The final acidity of step b) preferably is controlled at pH8.C) alkali lye described in is NaOH or potassium hydroxide, is preferably 1: 1.05 with the carboxylic acid mol ratio.

Technical solution of the present invention further comprises described petroleum carboxylate surfactant as the application of oil displacement agent in tertiary oil recovery, and as the composite dose of application in tertiary oil recovery.

The present invention includes following accompanying drawing:

Fig. 1 is a petroleum carboxylate preparation technology flow chart of the present invention;

Fig. 2 is the INTERFACIAL TENSION CURVES figure at the interface of petroleum carboxylate of the present invention and crude oil;

Fig. 3 is petroleum carboxylate of the present invention and the active figure of sulfonate compound system.

Below with reference to the drawings and specific embodiments, describe in detail technology contents of the present invention with and the significant technique effect that brings.

Embodiment one,

According to petroleum carboxylate flow process (Fig. 1): the distillate double centner that with molecular weight is 280 Daqing crude oil places stills for air blowing, be warming up to 200 ℃ and add catalyst, be blown into compressed air from the air distributor that is positioned at the stills for air blowing bottom, continue to be warmed up to 200 ℃ of oxidizing temperatures simultaneously.Keep temperature stabilization in course of reaction, its control device can be led to chilled water (chw) for adopting the steam aperture in the coil pipe in the stills for air blowing as emergency in coil pipe.

Every the acidity of 1 timing reactant, when reaching pH8, lower the temperature and stop compressed air in the course of reaction, at this moment, oxidation reaction is finished; Oxidation product is moved into saponification still about 100 degree, add 30% NaOH of double centner, stirred 1 hour, system is left standstill; To leave standstill back lower floor soap lye and emit, and under 60 degree conditions, add the breakdown of emulsion collection and carry out the breakdown of emulsion processing, remove the oil of solubilising, obtain the product petroleum carboxylate.Leave standstill the oil of liquid upper strata, separable back recycle feed for reaction.

Embodiment two,

With the technological process of embodiment one, wherein, raw materials used is 380 distillate for molecular weight;

Oxidizing temperature is 140 degree, and oxidation acidity final value is pH9, adds 110 kilograms 40% potassium hydroxide solution during saponification.

Embodiment three,

With the technological process of embodiment one, wherein, raw materials used is the fraction oil of molecular weight 400;

Oxidizing temperature 100, oxidation acidity final value is pH8.

Embodiment four,

With the technological process of embodiment two, wherein, oxidizing temperature is 120 degree, and the pH value is 8,

The NaOH that adds 120 kilogram 20% during saponification.

The petroleum carboxylate of the present invention of the foregoing description one to four preparation is formed, measures with column chromatography, and analytical method such as following, it the results are shown in table 1

Table 1

Experiment number	Saturated hydrocarbons %	Aromatic hydrocarbons %	Ester %	Alcohol %	Carboxylic acid %	Strong polarity thing %	Yield %
								Embodiment 1	48.54	3.05	4.22	15.45	11.67	17.06	97.29
Embodiment 2	43.70	9.73	4.29	15.82	10.58	17.82	97.48
								Embodiment 3	47.65	3.07	3.66	15.50	10.22	19.90	99.42
Embodiment 4	45.2	4.09	3.88	15.68	11.04	18.92	98.50

Adopt aluminium oxide-silica gel column chromatography that the hydrocarbon oxidation product is formed and analyze, it has sample and amount of reagent is few, repeatability advantage preferably.Existing division is as follows:

1, principle

Column chromatography is to make adsorbent with solid matters such as silica gel, aluminium oxide, with appropriate solvent drip washing separating mixture.Adsorbent is the material with certain polarity, and the adsorption capacity of sample strengthens with its molecular polarity.Because adsorbent to the absorption affinity difference of each group in the separated mixture, can be issued to the purpose of separating mixture component in appropriate solvent drip washing.

2, adsorbent

With neutral alumina 400 ℃ of activation 4 hours in muffle furnace, with silica gel 140 ℃ of activation 4 hours in baking oven, the silica gel that activation is good, aluminium oxide stir evenly by ratio mixing in 3: 1 that to put into drier standby.

3, eluent

Earlier begin wash-out, increase solvent polarity then gradually with a kind of non-polar solven, make separated mixture by nonpolar, low pole, strong polarity, by force polarity, the order of strong polarity is reached the separation purpose by wash-out.The situation that heavily is about 300mg for column length 45cm, sample, we use benzinum 60ml wash-out saturated hydrocarbons earlier, benzene-benzinum (2.5: 1) 60ml wash-out aromatic hydrocarbons, ether-benzinum (1: 9) 80ml wash-out ester (ketone), formic acid-ether (1: 99) 120ml wash-out carboxylic acid, the strong polarity thing of formic acid-ethanol (3: 97) 100ml wash-out.

4, measure material concentration in each eluent respectively, obtain the composition of petroleum carboxylate product.

Embodiment five, petroleum carboxylate of the present invention application-be used for tertiary oil recovery as oil displacement agent

In the foregoing description product petroleum carboxylate, find behind the electrolyte of adding higher concentration:

Petroleum carboxylate (POS) can be at surfactant concentration scope and the salinity scope and the crude oil generation ultralow interfacial tension of broad.Fig. 2 is that (electrolyte concentration is in the system: Na with the INTERFACIAL TENSION CURVES of crude oil for the POS (POS valid density is about 10%) of variable concentrations ₂CO ₃1.2%, NaCl1.0%).As can be seen, reach at 0.05% o'clock and can reach ultralow interfacial tension with crude oil in that commodity concentration is low, petroleum carboxylate of the present invention can reach the technical indicator of tertiary oil recovery as oil displacement agent.

The present invention measures the interfacial tension instrument and drips interfacial tensimeter for the Model-500 type rotation that Texas ,Usa university produces, and experimental temperature is 45 ℃.

The application of embodiment six, petroleum carboxylate of the present invention-composite alkylbenzenesulfonate is used for tertiary oil recovery

Petroleum carboxylate and alkylbenzenesulfonate is composite, and compound system reaches ultralow interfacial tension as a result, and test shows:

(1) petroleum carboxylate and sulfonate (MS-45) have good complementary effect in composite:

When MS-45 is 0.125% in concentration, NaOH concentration is under 1.2% the situation and the interfacial tension of crude oil is 8.09 * 10 ^-2MN/m; Carboxylate is 1% in concentration, NaOH concentration is under 1.2% the situation and the interfacial tension of crude oil is 1.58 * 10 ^-2MN/m; All do not reach ultralow value; And their compound system (concentration of MS-45 is 0.125%, the concentration of carboxylate is 1%, NaOH concentration be under 1.2% the situation) and the interfacial tension of crude oil are 1.90 * 10 ^-3MN/m;

(2) MS-45 and carboxylate can obtain good composite effect in very big compound proportion scope.As can be seen from Table 2, in oil carboxylic complex salt if add minute quantity MS-45 can reach * 10 ^-3Or * 10 ^-4The interfacial tension of the mN/m order of magnitude this shows that MS-45 is the good auxiliary agent of carboxylate.(MS-45 (as 3: 1,5: 1) interfacial tension value when the compound system proportion is big is higher).

Table 2 carboxylate POS and the interfacial tension of sulfonate MS-45 compound system under different compound proportions

Compound proportion	3∶1	5∶1	8∶1	12∶1	16∶1	24∶1	48∶1	100∶1	200∶1	300∶1	2400∶1	100000∶1
													Carboxylate salt concentration %	1	1	1	1	1	1	1	1	1	1	1	1
Sulfonate concentration %	0.33	0.2	0.125	0.083	0.0625	0.0417	0.0208	0.01	0.005	0.0033	0.000417	0.0001
													Interfacial tension=10 -3mN/m	11.7	5.38	1.90	2.07	1.142	0.457	0.138	0.853	0.118	0.442	0.193	0.989

(3) compound system of carboxylate and sulfonate MS-45 can reach ultralow interfacial tension in the basicity and the concentration range of broad.As shown in table 3, when carboxylate and the composite ratio of MS-45 were 12: 1 (be that carboxylate salt concentration is 1%, sulfonate MS-45 concentration is 0.083%), compound system can be that the scope of 0.2-2.0% produces ultralow interfacial tension with grand celebration source oil in NaOH concentration.

Table 3

NaOH concentration %	0.0	0.2	0.4	0.6	0.8	1.2	1.6	2.0
									Interfacial tension mN/m	5.81×10 -4	7.03×10 -4	5.11×10 -4	9.99×10 -5	2.14×10 -4	2.07×10 -3	1.22×10 -4	4.67×10 -3

Fig. 3 is the activity figure of above-mentioned compound system, and this system interfacial tension under low basicity is very low as can be seen from activity figure, still can produce ultralow interfacial tension in the surfactant concentration scope of broad when NaOH concentration is 0.As can be seen, if with carboxylate salt concentration is 1%, sulfonate MS-45 concentration is 0.083%, NaOH concentration be 0.8% or 0.6% system as injection system, when surfactant concentration and the bigger amplitude of alkali concn being reduced, still can keep high interfacial activity in stratum dilution, absorption, reaction.This system is 0 o'clock a low interfacial tension in low basicity even basicity, might reduce the alkalinity of compound system greatly, and basicity is low, interfacial activity keeps, polymer viscosity is kept favourable advantage thereby have in three-component compound system.This system can be under the situation of exogenously added alkali not and crude oil reach ultralow interfacial tension, have bigger using value for the surfactant flooding in oil field.

Embodiment six compound systems have been carried out displacement of reservoir oil performance test, adopted artificial core and simulated formation water, inject water.Test method is as follows, the results are shown in Table 4:

Carried out the oil displacement test of petroleum carboxylate compound system with the artificial core (artificial core is the diamond spar sand that phosphorus is joined the aluminium glue knot, and research institute buys by Jianghan Oil-field) of φ 2.5cm * 8cm.The used crude oil of oil displacement test is recover the oil four factory's degassed crudes and join a station crude oil of grand celebration; Institute's water injects the Simulated Water that water ion is formed preparation for four factories of recovering the oil by grand celebration, and its total salinity is 4910.97mg/l.The compound proportion of experiment 1,2,3 PetroChina Company Limited.'s carboxylates and sulfonate (MS-45) is 16: 1, oil displacement efficiency average out to 16.04%.The compound proportion of experiment 4,5,6,7,8 PetroChina Company Limited.'s carboxylates and MS-45 4: 1, oil displacement efficiency average out to 19.16%.

The oil displacement test of table 4 petroleum carboxylate compound system on artificial core

The experiment number			1	2	3	4	5	6	7	8
											Initial oil saturation (%)			75.5	76.6	73.3	72.1	76.8	71.7	77.3	69.9
Injection rate (cm/h)			18	18	18	18	18	18	18	18
											Compound system is formed	Carboxylate/MS		16	16	16	4	4	4	4	4
MS/(％wt％)		0.075	0.05	0.875	0.2	0.15	0.2	0.2	0.25
										Carboxylate (wt%)		1.2	0.8	1.4	0.8	0.6	0.8	0.8	1.0
NaOH		1.2	1.2	1.2	1.2	1.2	1.2	1.2	1.2
										HPAM(ppm)		1500	1500	1500	1500	1500	1800	1200	15OO
Viscosity (mPas)			10.2	10.2	10.2	10.2	10.2	15.2	5.2											10.2
										Interfacial tension mN/m		Instantaneous minimum (10 -3)	5.80	3.67	9.77	0.886	1.26	3.22	1.14		5.95
Before the steady-state value displacement of reservoir oil (10 -3)	7.98	4.12	29.6	0.886	4.62	4.93	1.97	6.73
									After the steady-state value displacement of reservoir oil (10 -3)						4.46	34.4	6.64	2.96	4.74
Waterflood recovery efficiency factor (OOIP%)			63.0	56.99	57.1	58.0	59.4	61.1												66.8	66.8
									Chemical displacement of reservoir oil efficient		OOIP％	17.71	14.51	17.70	19.15	17.19	21.18	16.61	21.58
Sor％	47.89	33.73	43.75	45.57	40.24	53.09	45.10	65.10
											Final oil displacement efficiency (OOIP%)			80.73	71.50	74.80	77.13	76.57	82.26	83.17	88.42

Claims (10)

1. With the preparation of following method, the petroleum carboxylate surfactant of molecular weight between 380-500, described preparation method may further comprise the steps:

   A) select C ₁₀-C ₂₈Between distillate feedstock;

   B) oxidation-oxidizing temperature is 100-200 ℃, and the duration is 2-8 hour

   The pH value was 8-9 when oxidation was finished;

   C) saponification-under 80-120 ℃, with the alkali lye of 20-40%, the mol ratio of alkali and oil carboxylic acid is 1: 1-1: 1.2 transfer to the pH value for 8-9, obtain petroleum carboxylate solution;

   D) separation, breakdown of emulsion obtain the product petroleum carboxylate.
2. 2. petroleum carboxylate surfactant according to claim 1 is characterized in that, the raw material molecular weight is 280-400 in described preparation method's step a).
3. 3. petroleum carboxylate surfactant according to claim 1 is characterized in that, raw material is preferably the second line of distillation distillate in described preparation method's step a).
4. 4. petroleum carboxylate surfactant according to claim 1 is characterized in that, alkali lye is NaOH or potassium hydroxide described in described preparation method's step c).
5. 5. the preparation method of the described petroleum carboxylate surfactant of claim 1 may further comprise the steps:

   A) select C ₁₀-C ₂₈Between distillate feedstock;

   B) oxidation-oxidizing temperature is 100-200 ℃, and the duration is 2-8 hour

   The pH value was 8-9 when oxidation was finished;

   C) saponification-under 80-120 ℃, with the alkali lye of 20-40%, the mol ratio of alkali and oil carboxylic acid is 1: 1-1: 1.2 transfer to the pH value for 8-9, obtain petroleum carboxylate solution;

   D) separation, breakdown of emulsion obtain the product petroleum carboxylate.
6. 6. the preparation method of petroleum carboxylate surfactant according to claim 5 is characterized in that, the raw material molecular weight is at 280-400 in the step a).
7. 7. the preparation method of petroleum carboxylate surfactant according to claim 5 is characterized in that, raw material is preferably the second line of distillation distillate in the step a).
8. 8. the preparation method of petroleum carboxylate surfactant according to claim 5 is characterized in that, alkali lye described in the step c) is NaOH or potassium hydroxide.
9. 9. the described petroleum carboxylate surfactant of claim 1 is as the application of oil displacement agent in tertiary oil recovery.
10. 10. the described petroleum carboxylate surfactant of claim 1 is as the composite dose of application in tertiary oil recovery.

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