CN104292385A - Method for preparing heat resistance and salt tolerance molecular surfactant - Google Patents

Abstract

The invention discloses a method for preparing a heat-resistance and salt-tolerance molecular surfactant, and in particular discloses a method for preparing a heat resistance and salt tolerance molecular surfactant, namely, polyacrylamide-2-acrylamide-2-methyl propanesulfonic acid-octadecyl acrylate P. The method comprises the following steps: by taking acrylamide, 2-acrylamide-2-methyl propanesulfonic and octadecyl acrylate in an appropriate mole ratio as raw materials, taking a certain amount of lauryl sodium sulfate as an emulsifier in a neutral solution and forming an oxidation reduction initiation system from a proper amount of ammonium persulfate and sodium hydrogen sulfite, triggering reaction at the temperature less than 50 DEG C, and synthesizing a high molecular surfactant P (AM-AMPS-SA) by using a micelle polymerization method. The raw materials used in the method are cheap and easy to obtain, the production cost is low, the operation method is simple and feasible and a product is high in viscosity, good in heat resistance and salt tolerance, high in oil expelling efficiency in indoor experience, superior in performance when being compared with polyacrylamide and macromolecule used in the Shengli Oil Field on site, and has the possibility of being used in oil fields.

Description

A kind of preparation method of temperature-resistance salt-tolerance macromolecular surfactant

Technical field

The invention belongs to technical field of oilfield chemistry, relate to a kind of preparation method of polymeric surface active agent, specifically, relate to a kind of preparation method of temperature-resistance salt-tolerance macromolecular surfactant.

Background technology

China's main oilfield as grand celebration, triumph, the Liaohe River etc., through once with still have the crude oil of 60%-70% to be retained in stratum after secondary oil recovery, but now the water content of oil reservoir is high, and oil recovery condition is harsher: hyposmosis, high temperature, high salt etc.In view of the reservoir characteristic that China is special, the main chemical flooding method that adopts improves tertiary oil recovery recovery ratio.Wherein, polymkeric substance and tensio-active agent improve the chemical oil displacement agent that recovery ratio amplitude is comparatively large, applicable surface is comparatively wide, cost is lower, tool grows a lot potentiality.Chromatographic separation phenomenon in driving owing to can avoid polymer-surfactant and have tackifying and surfactivity concurrently, polymeric surface active agent is the chemistry agent having application prospect in tertiary oil recovery technology.And to raising oil recovery factor, there is important practical significance for the polymeric surface active agent that the harshness oil recovery condition development of current China high temperature and high salt has a heat-resistant salt-resistant performance especially.

Summary of the invention

In order to overcome the defect existed in prior art, the invention provides a kind of preparation method of temperature-resistance salt-tolerance macromolecular surfactant, is that one is prepared and had high viscosity, the method for the polymeric surface active agent of superior heat-resistant salt-resistant performance.

Its technical scheme is as follows:

A preparation method for temperature-resistance salt-tolerance macromolecular surfactant, comprises the following steps:

(1) take AMPS, after adding appropriate distilled water wiring solution-forming, be adjusted to pH=7 by NaOH solution;

(2) take AM, be dissolved in the AMPS solution of modulated good pH;

(3) in solution, add sodium lauryl sulphate SDS again, after stirring, add the SA of set amount again, add distilled water and make monomer content in solution reach set(ting)value, with high-speed shearing emulsion machine, emulsifying soln is even under 40 DEG C of water-baths;

(4) solution dissolved is led to nitrogen 30min, to remove the dissolved oxygen in solution;

(5) add initiator ammonium persulfate and sodium bisulfite in the solution, stir in being placed at 45 DEG C water bath with thermostatic control and fully react, obtain clear gum polymkeric substance;

(6) wash away unreacted monomer in product with dehydrated alcohol, absorb most of moisture and be placed on oven dry at 50 DEG C in vacuum drying oven, pulverizer is pulverized, and obtains white powder and is the finished product.

Further preferably,

Wherein when best proportion is as follows:

the above part is mass fraction.

Now products obtained therefrom viscosity is the highest, and in salts solution, heat resistance and salt tolerance is the strongest, and heat-resistant salt-resistant performance is best.

Compared with prior art, beneficial effect of the present invention:

(1) the polymeric surface active agent molecular weight prepared by is higher, and viscosity is large, and the polymeric surface active agent that heat-resistant salt-resistant performance all uses than industrial polypropylene acid amides and Oil Field is superior; (2) polymeric surface active agent that the polymeric surface active agent oil displacement efficiency prepared by laboratory experiment proof uses compared with industrial polypropylene acid amides and Oil Field is superior; (3) use raw material cheap and easy to get, production cost is low.

Accompanying drawing explanation

Fig. 1 is the reaction equation of the preparation method of temperature-resistance salt-tolerance macromolecular surfactant of the present invention;

Fig. 2 is the infrared spectrum of monomer A M.

(1) 3342cm-1 place is N-H stretching vibration peak, and 1608cm-1 is N-H flexural vibration, 1426cm-1C-N stretching vibration peak, and 1672cm-1 is C=O stretching vibration peak, there is amide group in interpret sample molecular structure; (2) 3095,3020cm-1 place is that unsaturated C-H shrinks vibration, and 1640cm-1 place is a substituted olefine C=C stretching vibration, the C=C key containing Asymmetrical substitute in interpret sample molecule.(3) amido linkage and double bond strength similarity, it is described, and content is substantially identical in the molecule.

Fig. 3 is the infrared spectrum of monomer A MPS.

(1) 3435cm ^-1place is N-H stretching vibration peak, 1608cm ^-1for N-H flexural vibration, 1549cm ^-1c-N stretching vibration peak, 1666cm ^-1for C=O stretching vibration peak, in interpret sample molecular structure, there is amide group; (2) 3090-3030cm ^-1place vibrates, at 1666cm for unsaturated C-H shrinks ^-1locate a substituted olefine C=C stretching vibration, the C=C key containing Asymmetrical substitute in interpret sample molecule; (3) 2945,2985cm ^-1place is the stretching vibration peak of saturated c h bond, 1409,1368cm ^-1for tertiary butyl division peak, illustrate in molecular chain to there is the tertiary butyl; (4) 1246cm ^-1, 1087cm ^-1, 627cm ^-1and 540cm ^-1place's absorption peak is sulfonic characteristic peak.

Fig. 4 is the infrared spectrum of monomer SA.

As seen from the figure: (1) 1724cm ^-1there is the C=O stretching vibration absorption peak of unsaturated ester in place, 1193cm ^-1, 1064cm ^-1place is the flexural vibration peak of C-O-C, there is ester in interpret sample molecule; (2) 1636 is the stretching vibration peak of C=C, 977cm ^-1place has occurred that the flexural vibration of alkene hydrogen in C=C double bond absorb, 3030cm ^-1place is the alkene hydrogen stretching vibration absorption peak of CH2=CH-COOR, and interpret sample molecule is unsaturated ester; (3) near 2900cm-1, strong absorption peak is the stretching vibration absorption peak of saturated C-H, and at 720cm ^-1there is (CH in place ₂) absorption peak of n chain link (n>4), interpret sample molecule is unsaturated Long carbon chain ester class.

Fig. 5 is the infrared spectrum of polymerisate P (AM-AMPS-SA).

(1) 3070cm ^-1the unsaturated c h bond stretching vibration peak at place disappears, 2973cm ^-1place occurs illustrating that reactant double bond is opened, polymerization reaction take place by the saturated C-H stretching vibration absorption peak that intensity is larger; (2) 3424cm ^-1place is N-H stretching vibration peak, 1666cm ^-1for the C=O stretching vibration peak of acid amides, 1543cm ^-1for N-H flexural vibration, 1450cm ^-1c-N stretches, and there is amide group in interpret sample molecular structure; (3) 1191cm ^-1, 1042cm ^-1, 627cm ^-1and 532cm ^-1place's absorption peak is sulfonic characteristic peak, containing sulfonic acid group in interpret sample molecular structure.(4) 2929cm-1 is the stretching vibration peak of saturated C-H in SA, l724cm ^-1place is the C=O stretching vibration peak of ester, and 1207 places are the C-O-C stretching vibration peak of ester, 720cm ^-1there is (CH in place ₂) _nthe absorption peak of chain link (n>4).Illustrate that octadecyl acrylate hydrophobic group SA has been introduced in the molecular chain of multipolymer.

Fig. 6 is the contrast of Ubbelohde viscosity under each polymeric surface active agent solution differing temps of same concentration.

Fig. 7 is the Ubbelohde viscosity retention rate after each polymeric surface active agent solution of same concentration places 24h at different temperatures.

Fig. 8 is that the Ubbelohde viscosity with each polymeric surface active agent solution of concentration after different time is placed at 90 DEG C changes.

Fig. 9 changes with the Ubbelohde viscosity of each polymeric surface active agent solution of concentration under different salinity.

Figure 10 is the surface tension of each polymeric surface active agent.

Figure 11 is the dynamical interfacial tension figure of each polymeric surface active agent aqueous solution.

Figure 12 is the dynamical interfacial tension figure of each polymeric surface active agent salts solution.

Figure 13 is the contrast of each polymeric surface active agent indoor displacement test core holding unit inlet pressure.

Embodiment

Technical scheme of the present invention is further illustrated below in conjunction with specific embodiment.

Embodiment 1

(1) accurately take 20.70gAMPS to be dissolved in 40ml distilled water, regulate pH=7 with sodium hydroxide solution;

(2) accurately take 28.40gAM, be dissolved in the AMPS solution of modulated good pH;

(3) accurately take 17.68gSDS, join in above-mentioned solution, stir;

(4) accurately take 0.81gSA, add appropriate distilled water and make monomer content in solution reach 10%, with high-speed shearing emulsion machine, emulsifying soln is even under 40 DEG C of water-baths;

(5) solution dissolved is transferred in there-necked flask, logical nitrogen 30min, the dissolved oxygen in removing solution;

(6) accurately take ammonium persulphate and each 0.075g of sodium bisulfite, add in reaction soln, the water bath with thermostatic control after stirring, there-necked flask being placed in 45 DEG C is fully reacted, and obtains clear gum polymkeric substance;

(7) wash away unreacted monomer in product with dehydrated alcohol, absorb most of moisture and be placed on oven dry at 50 DEG C in vacuum drying oven, pulverizer is pulverized, and obtains white powder and is the finished product.

Embodiment 2

(1) accurately take 10.35gAMPS to be dissolved in 20ml distilled water, regulate pH=7 with sodium hydroxide solution;

(2) accurately take 28.40gAM, be dissolved in the AMPS solution of modulated good pH;

(3) accurately take 15.50gSDS, join in above-mentioned solution, stir;

(4) accurately take 0.73gSA, add appropriate distilled water and make monomer content in solution reach 10%, with high-speed shearing emulsion machine, emulsifying soln is even under 40 DEG C of water-baths;

(5) solution dissolved is transferred in there-necked flask, logical nitrogen 30min, the dissolved oxygen in removing solution;

(6) accurately take ammonium persulphate and each 0.059g of sodium bisulfite, add in reaction soln, the water bath with thermostatic control after stirring, there-necked flask being placed in 45 DEG C is fully reacted, and obtains clear gum polymkeric substance;

(7) wash away unreacted monomer in product with dehydrated alcohol, absorb most of moisture and be placed on oven dry at 50 DEG C in vacuum drying oven, pulverizer is pulverized, and obtains white powder and is the finished product.

Embodiment 3

(1) accurately take 20.70gAMPS to be dissolved in 20ml distilled water, regulate pH=7 with sodium hydroxide solution;

(2) accurately take 28.40gAM, be dissolved in the AMPS solution of modulated good pH;

(3) accurately take 17.68gSDS, join in above-mentioned solution, stir;

(4) accurately take 0.57gSA, add appropriate distilled water and make monomer content in solution reach 10%, with high-speed shearing emulsion machine, emulsifying soln is even under 40 DEG C of water-baths;

(5) solution dissolved is transferred in there-necked flask, logical nitrogen 30min, the dissolved oxygen in removing solution;

(6) accurately take ammonium persulphate and each 0.075g of sodium bisulfite, add in reaction soln, the water bath with thermostatic control after stirring, there-necked flask being placed in 45 DEG C is fully reacted, and obtains clear gum polymkeric substance;

(7) wash away unreacted monomer in product with dehydrated alcohol, absorb most of moisture and be placed on oven dry at 50 DEG C in vacuum drying oven, pulverizer is pulverized, and obtains white powder and is the finished product.

Table 1

Table 2

Table 3

The polymeric surface active agent that product P (AM-AMPS-SA) and now widely used polyacrylamide and oil field use is compared, can find that its viscosity-average molecular weight is close with it by table 1, reach 1,680 ten thousand.Determine the dissolution time in water under each polymer normal temperature, by table 2 can find industrial PAM due to granularity comparatively large, dissolution time is the longest, is 5h; P (AM-AMPS) and P (AM-AMPS-AE) dissolution time the shortest, only need 2h.Each polymer is made into the aqueous solution that concentration is 0.15%, investigates its heat-resistant salt-resistant performance and surfactivity.The heat resistance that can be found polymer P (AM-AMPS-SA) by Fig. 6 and Fig. 7 is best, and at 120 DEG C, its Ubbelohde viscosity still can remain on more than 1000ml/g, and its 70 DEG C and 90 DEG C time viscosity retention rate reach more than 90%.Each polymer 0.15% aqueous solution is placed one week at 90 DEG C, measure respectively and place 1d, 3d, 5d, solution viscosity after 7d, contrast with untreated solution, can find that polymer P (AM-AMPS-SA) substantially maintains this higher scope of 2500ml/g after decline by Fig. 8, another three sample viscosity are less.Measure salinity be respectively 20000,15000,10000,7500,5000,2000, the Ubbelohde viscosity of each macromolecular solution 70 DEG C time of 1000mg/L, P (AM-AMPS-SA) can be found by Fig. 9.Its aqueous solution Ubbelohde viscosity can reach 2882ml/g, is increased to its viscosity in 2000mg/L process constantly increases and reach the highest 3718ml/g in scope of experiment in NaCl concentration.Measure the surface tension at each high molecular 20 DEG C, by Figure 10 can find polyacrylamide and and P (AM-AMPS) almost there is no surfactivity, P (AM-AMPS-SA) is then close with the high molecular form surface tension of Oil Field, reaches 52mN/m.Investigate at each polymer 70 DEG C 0.10% the aqueous solution and salinity be the salts solution of 2000mg/L and interfacial tension between Gudong crude oil, can find that between industrial PAM and crude oil, interfacial tension exceeds instrument range by Figure 11 and Figure 12.P (AM-AMPS) after composite with 1:1 with SDS and polymer P (AM-AMPS-AE) is basically stable at about 7mN/m with the interfacial tension of crude oil in aqueous, show good interfacial activity, in salts solution, be then elevated to 10-20mN/m.0.15% aqueous solution is used for indoor displacement test, can find that P (AM-AMPS-SA) displacement equilibrium pressure is maximum by Figure 13 and table 3; Improve recovery ratio amplitude the highest, reach 29.5%, performance is better than the polymer of polyacrylamide and Oil Field use.

The above, be only best mode for carrying out the invention, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses, and the simple change of the technical scheme that can obtain apparently or equivalence are replaced and all fallen within the scope of protection of the present invention.

Claims (3)

1. a preparation method for temperature-resistance salt-tolerance macromolecular surfactant, is characterized in that, comprises the following steps:

(1) take AMPS, after adding appropriate distilled water wiring solution-forming, be adjusted to pH=7 by NaOH solution;

(2) take AM, be dissolved in the AMPS solution of modulated good pH;

(3) in solution, add sodium lauryl sulphate SDS again, after stirring, add the SA of set amount again, add distilled water and make monomer content in solution reach set(ting)value, with high-speed shearing emulsion machine, emulsifying soln is even under 40 DEG C of water-baths;

(4) solution dissolved is led to nitrogen 30min, to remove the dissolved oxygen in solution;

(5) add initiator ammonium persulfate and sodium bisulfite in the solution, stir in being placed at 45 DEG C water bath with thermostatic control and fully react, obtain clear gum polymkeric substance;

(6) wash away unreacted monomer in product with dehydrated alcohol, absorb most of moisture and be placed on oven dry at 50 DEG C in vacuum drying oven, pulverizer is pulverized, and obtains white powder and is the finished product.

2. the preparation method of temperature-resistance salt-tolerance macromolecular surfactant according to claim 1, is characterized in that,

3. the preparation method of temperature-resistance salt-tolerance macromolecular surfactant according to claim 2, is characterized in that,