CN101612537B - Functional macromolecule surfactant and application thereof - Google Patents
Functional macromolecule surfactant and application thereof Download PDFInfo
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- CN101612537B CN101612537B CN2009100554942A CN200910055494A CN101612537B CN 101612537 B CN101612537 B CN 101612537B CN 2009100554942 A CN2009100554942 A CN 2009100554942A CN 200910055494 A CN200910055494 A CN 200910055494A CN 101612537 B CN101612537 B CN 101612537B
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Abstract
The invention relates to a functional macromolecule surfactant with the general formula (1); wherein, R1, R2, R3 and R4 are separately selected from H, sulfhydryl group, phenyl group, sulfonic group, benzenesulfonic acid group, nitrogen-containing sulfydrylheterocycle, quaternary ammonium salt, iminazole or thiophene. The macromolecule surfactant is applicable to oil exploitation, oil-contained sewage treatment, oil-contained sludge treatment, oil-contained seawater treatment, seawater purification and the like.
Description
Technical field
The present invention relates to petrochemical industry, be specifically related to a kind of functional macromolecule surfactant and uses thereof, this high molecular surfactant is applicable to oil recovery, oily waste water treatment, oily sludge processing, oil-containing Seawater Treatment or seawater cleaning or the like.
Background technology
Up to now, China and even most of in the world large-scale oil fields have all experienced blowing and two mining phases of water drive.Generally, at the oil exploitation initial stage, just utilize the natural energy recover petroleum on stratum, be called primary oil recovery, its recovery ratio is merely about 10%.Secondary oil recovery is meant the method for coming recover petroleum through to the stratum makeup energy, like water filling, gas injection etc.After experiencing these two mining phases, crude output all has successively decreasing in various degree, and exploration cost and difficulty are also increasing.Data show, rely on present existing technology, and the average recovery ratio in oil field has only 32.2%, also have surpass 2/3 crude oil be trapped in underground can't extraction.For this reason, develop multiple technologies in the oil exploitation industry again, exploited the crude oil of retention, be called tertiary recovery.Particular type is described below.
(1) the gas displacement of reservoir oil, representative recovery method is a carbon dioxide drive, its mechanism of oil displacement is an injecting carbon dioxide in oil reservoir, plays the crude oil that in oil reservoir, expands, reduces viscosity of crude, thereby the effect of displacement crude oil.
This technological defective is: ground surface works equipment drops into too high, needs the huge investment gas pipeline, and running cost is too high with the safety measure input.Often lack enough carbon dioxide air sources near many oil fields, very strong hysteresis quality is being arranged aspect the effect of gathering.
(2) microbial oil displacement, its mechanism of oil displacement is: inject suitable bacterial classification and nutrients to oil reservoir, bacterial strain is bred in oil reservoir, the metabolism oil produces gas or active material, can reduce oil water interfacial tension, to improve oil recovery.
This technological defective is: technology is still immature.Microorganism receives such environmental effects extremely many, and it is very slow therefore to take effect, the inefficiency of gathering.
(3) oil recovery by heating, its representative recovery method is a steam soak.Steam soak makes periodically steam injection, steam immersion, steam swash product etc. again, mainly is the production technique that improves recovery ratio to heavy crude reservoir.So-called steam soak is exactly to inject a certain amount of steam to oil well earlier, closing well a period of time, the heat energy of treating steam after the oil reservoir diffusion, a kind of raising the output method of exploiting heavy oil of opening well and making production again.
This technological defective is: ground surface works equipment and safety devices drop into huge, and the operation operation cost is too high.
(4) chemical displacement of reservoir oil, its representative recovery method is a polymer displacement of reservoir oil, its mechanism is: polymer flooding mainly by increasing displacing fluid viscosity, reduces the mobility ratio of displacing fluid and driven liquid, thereby enlarges swept volume; On microcosmic, polymer has increased the power of carrying because its intrinsic viscoplasticity produces the stretching action to oil film or oil droplet in flow process, has improved the microcosmic displacement efficiency.
This technological defective is: the injection allocation of ground system process is complicated, many and cause construction investment bigger with the pump amount.The regular job cost is high, and high molecular polymer heatproof not, and not anti-salt can't be used in high temperature, high salinity oil district.Output water injection allocation again in oil field must be fallen as sewage disposal.
Hence one can see that, and various tertiary oil recovery technologies or method all have its defective, in the industry still demand can improve the new method of oil recovery and rate of oil production, also require it to reduce simultaneously to pollute, the protection environment.
Summary of the invention
Thus, the purpose of this invention is to provide a kind of new type functional high molecular surfactant, it can improve oil recovery and rate of oil production, reduces pollution level, protection environment etc. simultaneously.
First aspect of the present invention relates to a kind of functional macromolecule surfactant, and it has general formula (1):
Formula (1)
R wherein
1Be selected from H, phenyl, benzene sulfonate; R
2Be selected from H, sulfydryl, nitrogenous sulfhydryl heterocycle; R
3Be selected from H, phenyl, nitrogenous sulfhydryl heterocycle, imidazoles, thiophene; R
4Be selected from quaternary ammonium salt.
In a preferred implementation, wherein said quaternary ammonium salt has functional group.Functional group is preferably selected from one or more in following: carboxylic acid group, sulfonic group, cycloalkyl, alkyl, pyridine, pyrroles, alkyl-carboxylic acid, sulfonic alkyl, cycloalkyl-alkyl, pyridine alkyl, pyrrolidinyl; Wherein said cycloalkyl is the cycloalkyl of 5 yuan or 6 yuan, and said alkyl is the alkyl of 3-18 carbon atom.Wherein said alkyl is the alkyl of 3-16 carbon atom preferably, is more preferably the alkyl of 8-16 carbon atom.
In another preferred implementation, described nitrogenous sulfhydryl heterocycle is a mercaptoimidazole.
In second aspect of the present invention; A kind of purposes that relates to functional macromolecule surfactant of the present invention; It is used for three oil exploitations, oily waste water treatment, oily sludge processing, oil-containing Seawater Treatment, seawater cleaning, or as drilling mud additives, textile industry processing aid, paper grade (stock) reinforcing agent, anti-clayswelling agent, adhesive, gap filler, flexibility agent, thinner or washing agent.
In a preferred implementation, high molecular surfactant of the present invention is used for three oil exploitations, oily waste water treatment, oily sludge processing, oil-containing Seawater Treatment or seawater cleaning.
Adopt new type functional high molecular surfactant of the present invention, can significantly improve oil recovery and rate of oil production.And very well, also very all of a sudden, it also is applicable to various conditions and the bad oil well of situation, for example: heavy crude reservoir, discarded oil well, oil-sand ore deposit, low-permeability oil deposit and high temperature, high salinity oil reservoir.It can be in meeting the scope of economic benefit, with the underground oil storage of disused well continuously, extraction farthest.
Description of drawings
Fig. 1 is the infared spectrum of the TBF-I high molecular polymer of preparation in the embodiment of the invention 1.
The specific embodiment
In functional macromolecule surfactant of the present invention, contain a plurality of substituting groups, comprising: R
1, R
2, R
3, R
4, sulfonic group, carboxylic acid group, amide groups.R wherein
1Be selected from H, phenyl, benzene sulfonate; R
2Be selected from H, sulfydryl, nitrogenous sulfhydryl heterocycle; R
3Be selected from H, phenyl, nitrogenous sulfhydryl heterocycle, imidazoles, thiophene; R
4Be selected from quaternary ammonium salt.
In these groups; Wherein said quaternary ammonium salt also preferably has functional group, is selected from: one or more in carboxylic acid group, sulfonic group, cycloalkyl, alkyl, pyridine, pyrroles, alkyl-carboxylic acid, sulfonic alkyl, cycloalkyl-alkyl, pyridine alkyl and the pyrrolidinyl.The cycloalkyl of wherein said cycloalkyl preferred 5 yuan or 6 yuan; The alkyl of the preferred 3-18 of a said alkyl carbon atom, the more preferably alkyl of 5-16 carbon atom, the alkyl of preferred 8-16 carbon atom again; The alkyl of preferred again 10-16 carbon atom, the preferred alkyl of 8-12 carbon atom again.
Formula (1)
In above-mentioned substituting group and functional group, cation group, anionic group and non-ionic group are arranged.They give high molecular surfactant with various functions and effect.Shown in the table specific as follows.
When wherein the alkyl of C8-C12 was contained in the functional group in the quaternary ammonium salt, anti-salt, anticalcium, magnesium ion, antibiont were degraded best; When containing the alkyl of C10-C16, the antibiont degraded is best.
When comprising benzene sulfonate in the substituting group, have anti-salt, anticalcium, magnesium ion performance, preferred P-TOLUENE SULFO ACID 99's base, better effects if.
When comprising phenyl in the substituting group, anti-salt, anticalcium, magnesium ion performance the best; During for sulfhydryl heterocycle, has anti-oxidant degradation property, preferred mercaptoimidazole base, its best results.
When comprising imidazoles, thienyl in the substituting group, anti-oxidant degradation property is best.
The high molecular surfactant that the present invention has above-mentioned substituting group and functional group has good function and effect.Especially in oil recovery, have following function and effect:
(1) has " four is anti-" function of the degraded of high temperature resistance, high salt tolerance and antibiont, anti-oxidant degraded, can be used for oilfield produced waste water preparation displacement solution;
(2) have " three height " function of efficient emulsification, efficient washing oil, efficient profile control, in the displacement process, can carry out automatically in order, realize the efficient displacement of reservoir oil;
(3) have and inject " two are prone to " function that well is prone to inject, the extraction emulsion is prone to breakdown of emulsion, be convenient to on-the-spotly use, running cost is low;
(4) the repeated monomer unit on its molecular backbone is identical one-component, can be called the monobasic chemical flooding, and essence is that macromolecule micelle drives, and can be used for tertiary oil recovery or gathers four oil recoveries after driving.
The existence of salt generally makes the viscosity of aqueous surfactant solution reduce.This is that end-to-end distance reduces because the ion of dissolving is curled strand, thereby viscosity increases with the concentration of salt and reduces.And the salt-resistance of surfactant of the present invention is achieved through following factor, can realize adopting sewage preparation displacement solution thus:
-sat linkage in utilizing
On the side group of hydrocarbon chain grafting the cationic surfactant and the electronegative anion surfactant of positively charged, form the hydrocarbon chain of both sexes.Because sat linkage in existing just can strengthen the ability of anti-salt and anti-high price calcium, magnesium ion during the sewage preparation;
-utilize the gathering of nonpolar side group
Nonpolar side group is not ion, and is insensitive for salt, and nonpolar side group is tending towards assembling self assembly each other in the aqueous solution, thereby solution viscosity can obviously increase;
-introduce dense ionization group sulfonate, quaternary ammonium salt etc., improve unit structure and character;
-suitable collateralization is promptly introduced substituent R 1-R4, increases chain rigidity.
The anti-oxidant degradation function of high molecular surfactant of the present invention is to realize through such mechanism.Generally speaking, oil increases aqueous solution viscosity under aerobic conditions of adopting surfactant and obviously descends, and oxidative cleavage is a wherein important reason; The mechanism of oxidative degradation is in this solution; Dissolved oxygen generates hydrogen peroxide, and hydrogen peroxide decomposes generates free radical OH, and free radical OH roams in solution, attacks; Make the surfactant chain rupture, the degraded chain reaction.The present invention introduces nitrogenous sulfhydryl heterocycle side group on the strand of surfactant, it is oxygen-transfer agent and peroxide decomposer in essence, and thus, effectively the peroxide in the decomposing solution suppresses chain rupture, realizes anti-oxidant degraded.In addition, functional group's pyridine and the pyrroles in substituting group imidazoles and thiophene and the quaternary ammonium salt also has anti-oxidant degradation.
The antibiont degradation function of high molecular surfactant of the present invention is to realize through such mechanism.Under oxygen free condition, biology enzyme can make macromolecular chain rupture, and in most cases side group fracture also can take place or changes, thereby causes the degraded of general polymer macromolecule, and solution viscosity is descended.The present invention has introduced quaternary ammonium salt group and sulfydryl etc. in the molecular structure of high molecular surfactant, they have the efficient sterilizing effect to sulfate reducing bacteria, thereby have the antibiont degradation characteristic.
Surfactant of the present invention can also be realized efficient profile control and strong water logging section selective water plugging.
Strong water logging section can occur in the Extra High Water Cut Stage in Oilfield reservoir, become the invalid cyclical field of water drive because its water phase permeability improves greatly.Owing to introduced hyperbranched cation group quaternary ammonium salt, chain alkyl (preferred 10-18 carbon atom) and cycloalkyl, make surfactant become a kind of selective shut-off agent in the high molecular surfactant of the present invention.When it got into water layer, said group was adsorbed on the sandstone surface that is washed away out by water, makes water layer by the hydrophilic oleophylic that changes into, has increased the flow resistance of water, plays plugging function.Its plugging function schematic diagram is as shown in Figure 1.
Because cation group and chain alkyl (preferred 10-18 carbon atom) and cycloalkyl are arranged in the molecular structure of this surfactant; Strengthen profile control if desired, can also further increase the carbon number of alkyl, increase alkyl chain length.It can be adsorbed in do not have basically oil; On electronegative strong water logging section and the rock surface,, not only changed the surface wettability (changing the strong oil-wet wetability into) of strong water logging section by strong hydrophilicity through multiple adsorb; Strengthened flow resistance, particularly the flow resistance at venturi position.
In addition, it is very high that the molecular weight of surfactant of the present invention can reach, and can reach about 10,000,000.Under the aqueous solution than high salinity, owing to hydrophobic effect, intermolecular curling winding effect in electrostatic interaction and the molecule, can form the structure of supramolecular aggregation, its bulk can reach tens microns or bigger.Therefore, " thief's layer " section can form very big flow resistance through multiple adsorb, reaches the purpose of profile control, stifled " thief's layer ".
The profile control method of surfactant of the present invention has long-lasting, and is more efficient more than the effect of general profile control agent.
Surfactant of the present invention can also be realized efficient viscosity reduction under the normal temperature.In this case; Need the molecular weight of this macromolecule surface agent alive is adjusted to very little (for example about about 20,000); The electrostatic repulsion of strong polar functional groups such as a large amount of carboxylic acid groups, sulfonate groups, quaternary amine group, self assembly is formed for the dispersion viscosity reduction stabilising system of viscous crude or conventional crude.So just can be in high concentration (more than the 1%) aqueous solution, viscosity reaches and approaches water, again can high degree of dispersion crude oil forms the emulsion of " profit dissolves each other " state, and the high viscosity heavy oil viscosity break ratio is reached more than 90%.
The viscosity-reducing mechanism of viscosity reduction type high molecular surfactant of the present invention when being applied to oil exploitation is:
-reducing viscosity by emulsifying: viscosity reduction type high molecular form agent solution alive fully mixes with thick oil underground well at a certain temperature, and making highly viscous crude is to be scattered in the thinner solution with thick oil droplet, forms low viscous oil-in-water (O/W) type emulsion, has reduced the resistance of motion of crude oil;
-breakdown of emulsion viscosity reduction: the agent of living of viscosity reduction type high molecular form can make the WO emulsion breakdown of emulsion and generate free water, forms " suspended oil ", " water floating oil " and viscosity reduction;
-absorption viscosity reduction: the viscosity reduction type high molecular form agent molecule of living is adsorbed on the tube wall or between oil reservoir and the resistance that reduces friction causes viscosity of crude significantly to descend.
The more important thing is that surfactant of the present invention can also be realized the efficient displacement of reservoir oil, the efficient displacement of reservoir oil is achieved by the ability of efficient solubilising and emulsified crude oil.
Surfactant of the present invention is introduced a large amount of nonionic oleophylic non-polar groups on the carbon-to-carbon flexible chain.Take into account the water-soluble of high molecular form agent alive,, introduced strong polarity hydrophilic radical again simultaneously: carboxylate, quaternary ammonium salt, sulfonate according to hydrophilic lipophilic balance (HLB value).This molecular structure has been confirmed the monobasic high molecular surfactant both for single component, has extremely strong amphiphilic (not only hydrophilic but also oleophylic) again.Under aqueous conditions, through in the molecule with intermolecular gathering, final form with the little micella of macromolecule to serve as the main supramolecular structure aggregation of forming, have the incomparable solubilising crude oil of conventional surfactants ability.
The preparation method of high molecular surfactant of the present invention is described below.
By stoichiometric ratio, with 3-R
1-2-propylene-1-sodium sulfonate, 1-R
3-acrylic acid, N-R
4-1-R
2-acrylamide, water and pH value conditioning agent join in the agitated reactor that molecular template is housed; Stirring mixes it, and adjustment pH is 5.8-6.2, and preferred 6.0; Feed inert gas (nitrogen, argon gas, helium etc.) protection; When being heated to 35 ℃-45 ℃ (preferred 38-42 ℃), stirring mixes it, and keeps more than 30 minutes-60 minutes (preferred 30-40 minute).Then, slowly add catalyst again, reacted preferred 3.0 hours 2.5-3.5 hour.Catalyst can adopt the conventional catalyst of synthetic polyacrylamide in the industry, preferred potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate.
Then, heat temperature raising is to 55-70 ℃, and preferred 65 ℃, adding pH value conditioning agent is regulated pH to 9-11, and preferred pH to 10 adds initator again, causes copolymerization 4.0-5.0 hour, and preferred about 4.5 hours, the reaction end.The high molecular polymer that obtains is a monobasic functional macromolecule surfactant of the present invention.Initator adopts the normal starter that synthetic polyacrylamide is used in the industry.
Adopt infrared spectrum to detect the structure of the surfactant product that obtains.3300cm wherein
-1, 1700-1720cm
-1Be carboxylic acid group's characteristic absorption; 3100-3000cm
-1, 1640-1650cm
-1About be the characteristic absorption of C=C key; 2910cm
-1, 2850cm
-1The peak at place is the characteristic absorption of chain alkyl methylene; 3200cm
-1, 1670cm
-1With 1190cm
-1About be the characteristic absorption of amide groups; 1380-1395cm
-1About be characteristic absorption of sulfonate or the like; The existence of these characteristic peaks shows in the molecular structure of target product and has groups such as carboxyl, two key, chain alkyl, amide groups and sulfonate.
The molecular template that uses in the reaction is synthetic special customization the as formula of the present invention (1) macromolecular compound.Its preparation process is following.
The preparation of molecular template: with 85% silica and 15% phenyl triethoxysilane homogeneous mixture is carrier, with 2-amino-4-nitrophenols as 3-R
1The identification molecule of-2-propylene-1-sodium sulfonate; With 1-methyl-2-(3-pyridine radicals) pyrrolidines as 1-R
3-acrylic acid identification molecule is N-R with the rhodamine B
4-1-R
2The identification molecule of-acrylamide.In the solution of 35% methyl alcohol, (alternative current 10mA, 30mA 80mA), make above-mentioned every kind of identification molecule be adsorbed on carrier surface with the unimolecule linear condition, and these three kinds identification molecules are alternately arranged regularly through electrochemical means.Then, drying and moulding forms molecular template.
The effect of molecular template is to utilize the molecule of respectively discerning on the template that synthetic high molecular corresponding kind monomer is played the target body effect.In polymerization process, molecular template guides the little molecule of various monomers to react in regular turn, forms macromolecule, and the The Nomenclature Composition and Structure of Complexes of decision product.
Molecular template polymerization principle is based on the interaction between the various molecular recognition unit of template and the little molecule of corresponding kind monomer that polymerization is used; Like the interaction of hydrogen bond, ion attraction, electron donor and acceptor or form covalent bond etc.; Create advantageous conditions for the micromolecular polymerization of monomer, realize orderly matrix polymerization.
Adopt above-mentioned molecular template of the present invention, just can access formula of the present invention (1) high molecular surfactant.
The method for using of molecular template: molecular template is prepared into the form of 5A molecular sieve, before using, soaks more than 1 hour with deionized water earlier, then, reinstall in the agitated reactor.After reaction finishes, molecular sieve is taken out activation, subsequent use.Can reuse 60-80 time.
Embodiment
The preparation of high molecular surfactant TBF-I:
Earlier the water with 1/3V (V is the effective volume of agitated reactor) joins in the agitated reactor that said molecular template is housed, example (1.0: 1.0: 1.0) in molar ratio, add 2-propylene-1-sodium sulfonate, acrylic acid, N-ethyl-(N '; N ' ,-dimethyl-N '-undecyl-(11 '-carboxylic acid) ammonium)-acrylamide, stirring is dissolved them fully; Then with pH value conditioning agent conditioned reaction solution; Making its pH is about 5.5, feeds nitrogen protection, when being heated to 42 ℃; Stirring mixes it, and keeps more than 30 minutes.Then, slowly add the catalyst potassium peroxydisulfate again, reacted about 3.0 hours.
About heat temperature raising to 68 ℃, add pH value conditioning agent, regulating pH is about 11.0, adds initator (ammonium persulfate-sodium sulfite) again, causes copolymerization about 5.0 hours, the reaction end.This product is a TBF-I monobasic functional macromolecule aqueous surfactant solution.Through super-dry, obtain powdered pure TBF-I product.
The mensuration of product TBF-I molecular weight:
Press GB12005.1-89 and G/T12005.10-92 national standard, use determination of ubbelohde viscometer.Use polyacrylamide inherent viscosity method determining molecular weight, in the NaCl of the 30 ℃ of following 1mol/L aqueous solution, measure its [η]=14.76mL/g, be calculated as follows its viscosity average molecular weigh M:
M＝802*[η]
1.25＝802*14.76
1.25＝23?202。
The infrared spectrum of TBF-I is referring to Fig. 1.
In Fig. 1,3421cm
-1, 1700cm
-1Be carboxyl characteristic absorption, 3421cm
-1Be the flexible vibrations of O-H key, 1700cm
-1Be the stretching vibration of C=O key; 3100-3000cm
-1, 1640cm
-1Be the characteristic absorption of C=C key, wherein 1640cm
-1The stretching vibration that is the C=C key absorbs 3100-3000cm
-1Be on the unsaturated carbon atom=the c h bond stretching vibration is included in the carboxyl characteristic peak; 2923cm
-1, 2850cm
-1The peak at place is the characteristic absorption of chain alkyl methylene; 3200cm
-1, 1668cm
-1With 1190cm
-1The peak be the characteristic absorption of amide groups, wherein 3200cm
-1Be the stretching vibration of N-H key, 1668cm
-1Be the stretching vibration of C=O key, 1190cm
-1Be that the stretching vibration of C-N key absorbs; 1384cm
-1Absworption peak for sulfonate; 1454cm
-1And 3400cm
-1More than two peaks corresponding to the nitrogen cation; The existence of these characteristic peaks shows in the molecular structure of target product and has carboxyl, hydroxyl, carbonyl, two key, amide groups, nitrogen cation, chain alkyl, sulfonate etc.
Testing experiment
The compatibility experimental data of TBF-I and stratum sewage (being the salt-resistance experiment)
In order to realize directly being configured to TBF-I solution with oilfield sewage, pollute thereby reduce, the protection environment carries out this compatibility experiment.Adopt the stratum sewage of 200000mg/L salinity to be mixed with the TBF-I solution that concentration is 1500mg/L, the result is as shown in the table.The test of absorbance A is: under 25 ℃,, under the 450nm condition, after placing different time, measure with spectrophotometer.
| Time (H) | Absorbance (A) | |
| 0 | 1.39 | 0 |
| 24 | 1.45 | 0.06 |
| 48 | 1.43 | 0.04 |
| 72 | 1.41 | 0.02 |
Δ A is the variation difference that absorbance increases in time in the last table, and its value is more little, shows that compatibility is good more.
Result of the test shows that Δ A value is very little, and absorbance increases in time big variation does not take place, and proves absolutely that the stratum sewage of TBF-I and 200000mg/L salinity is compatibility, has good " salt-resistance ".Can realize fully directly with oilfield sewage configuration TBF-I solution.
Sewage and the contrast of distilled water preparation TBF-I solution viscosity stability
The viscosity of TBF-I solution has a strong impact on the TBF-I oil displacement efficiency, so research sewage influences the TBF-I solution viscosity.Elder generation's water is mixed with concentration 5000mg/L mother liquor, uses extraction sewage and distilled water respectively with the TBF-I solution of mother liquor dilution as 1000mg/L and 1200mg/L then.Oxygen free condition is preserved down, regularly under 45 ℃ of conditions, measures viscosity with Brookfield viscometer, compares.
Result of the test shows, can directly prepare TBF-I solution with sewage, and to the not influence of its viscosity.Both practice thrift cost, protected environment again.
Influence detects data to anaerobic bacteria to TBF-I
In oilfield sewage, contain a large amount of bacteriums, have very strong bactericidal effect in order to confirm TBF-I, the spy carries out this experiment.Experimental result is as shown in the table.Disconnected west is a block of Daqing oil field.Disconnected western sewage is the sewage of taking from disconnected Westbound piece.Simultaneously, parallel bactericidal properties of having carried out the aqueous solution of conventional displacement of reservoir oil polymer-polyacrylamide.
Because introduced quaternary ammonium salt monomer in the TBF-1 molecular structure, quaternary surfactant has the efficient sterilizing effect to sulfate reducing bacteria, has the antibiont degradation characteristic.
TBF-I body viscosity data
The TBF-I viscosity in aqueous solution has decisive influence to the site construction technology flow process of TBF-I, so carry out TBF-I aqueous solution body Study on Viscosity.The result is as shown in the table.
| TBF concentration mg/ |
500 | 1000 | 1500 | 2000 | 5000 | 10000 | 15000 | 20000 |
| Viscosity mPa.s | 1.81 | 1.98 | 2.12 | 2.3 | 2.5 | 2.55 | 2.59 | 2.6 |
Experimental result explanation: the TBF-I aqueous solution is under high concentration (20000mg/L), and its viscosity is similar with the viscosity of water, constructs easily thus, injection technology is simple.
The experiment of TBF-I aqueous solution viscosity reduction
The TBF-I aqueous solution is big more to the viscosity reduction ability of crude oil, and oil displacement efficiency is strong more, and this experiment is in order to screen suitable TBF-I concentration of aqueous solution, to reach best viscosity reduction and oil displacement efficiency.The result is as shown in the table.
Experimental result proves:
-in the mixture of TBF solution and oil, TBF-I concentration is high, and viscosity break ratio is just high;
-in the mixture of TBF solution and oil, the ratio that crude oil accounts for is high, and viscosity reducing effect is just poor; Under 1: 1 situation of liquid oil ratio, viscosity break ratio >=95%;
-along with the prolongation of time, viscosity break ratio changes little, explains that solution has emulsifying capacity and good stability preferably;
The TBF-I viscosity reducing effect of-1000mg/L is poor, and the TBF-I viscosity reducing effect of 1500mg/L and 2000mg/L is similar.
TBF-I type and the contrast of common ternary system emulsifying effectiveness
Through TBF-I type and common ternary system emulsifying effectiveness contrast experiment to crude oil, prove the TBF-I type than conventional ternary oil displacement system (alkylbenzene xanthate, oil xanthate etc.), have better efficient solubilising and emulsified crude oil ability.
The Gravity Separation experiment of profit in capillary
Through the experiment of the crude oil Gravity Separation in the capillary, can prove that TBF-I has stronger permeability, can get into easily in the fine gap of formation rock, and the mother oil displacement in the slit is come out, improve oil displacement efficiency greatly.
When not adding TBF-I in the capillary, less than 4mm pipe gravitational differentiation difficulty, the 5mm pipe can differentiation through agitating.
When adding the TBF-I solution of 1500mg/L in the capillary, float to the top greater than the crude oil in the 2mm capillary on all, after 2 hours, the crude oil in the 1mm capillary almost floats to the top on all.
The rectangular homogeneous core of TBF type oil displacement experiment result
In order to prove the oil displacement efficiency of TBF, the spy carries out TBF-I and the ternary ASP of routine and the indoor displacement of reservoir oil contrast experiment of polyacrylamide.In this experiment flow, carry out water drive earlier, after water drive output liquid water content is greater than 98.5%, carry out polymer flooding, after the output liquid water content of polymer flooding is greater than 98.5%, carry out follow-up water drive again.Polymer flooding can be called polymer plug again.The recovery ratio raising value that polymer flooding adds follow-up water drive is called always to gather drives raising value %.Adopt TBF-I of the present invention and conventional ternary ASP and conventional polyacrylamide to experimentize respectively,, all carried out at least two parallel laboratory tests, with the reliability of test experience for every kind of polymer.
Experimental result proves:
-for the experiment of adopting with a kind of polymer, its data are more approaching, and good reproducibility is described, but comparative is strong;
-waterflood recovery efficiency factor is close, drives that recovery ratio raising value has difference in slug and the follow-up water drive but gather;
-annotating TBF-I can improve recovery ratio＞24%, and ultimate recovery can reach 75%, compares with ternary ASP combination flooding, can improve recovery ratio 6%.
Sudden and violent gas experiment
In order to confirm whether easily breakdown of emulsion of output liquid, and whether the oil behind the breakdown of emulsion, water two meet related request mutually, and the spy carries out aeration experiment.
The TBF-I aqueous solution of 1500mg/L is mixed with 1: 1,1: 2,1: 3 volume ratio with crude oil; Form emulsified solution; This emulsified solution mixes in the ratio of 1: 2 volume ratio with formation water again, and sudden and violent gas can find out after 4 hours that layering liquid becomes clearly gradually.Crude oil on the glass wall, also wall built-up not gradually.Explain that thinner can form water membrane between crude oil and rock, steel pipe, play good drag reduction washing oil effect.In addition, be easy to breaking emulsion and dewatering after the exploitation.
Upper strata after layering oil mensuration is moisture, lower layer of water is measured oil-containing, it is following to record data:
Moisture result sees from oil-containing, the dehydration of this thinner, demulsification reached the oil field with the standard of demulsifier (oil phase is moisture≤30%, water oil-containing≤240mg/L).
Gather and drive under the different recoverys percent of reserves in back, TBF drives the effect that improves recovery ratio
TBF of the present invention also has the good effect of such accident: after using the common conventional polymer displacement of reservoir oil, re-use the TBF displacement of reservoir oil, its recovery ratio can further improve.The inventor is for after studying conventional polymer and driving, and under different recovery percent of reserves conditions, TBF drives the influence that recovery ratio is improved, and the spy tests.Following table is that conventional polyacrylamide drives under the different recoverys percent of reserves in back, and TBF drives the recovery ratio effect comparison that is improved.
| Polyacrylamide drives the back recovery percent of reserves | TBF drives the back recovery percent of reserves | TBF drives the raising recovery ratio |
| 40.3％ | 58.5％ | 18.2％ |
| 49.5％ | 65.2％ | 15.7％ |
| 60.8％ | 72.3％ | 11.5％ |
Can find out from result of the test: polyacrylamide drive the back TBF drive raising recovery ratio＞10%, and gather drive the back recovery percent of reserves high more, the amplitude that TBF further improves recovery ratio is more little.
In sum, can know from above-mentioned result of the test:
-TBF-I and oil field stratum sewage compatible property are good, can be directly with the on-the-spot sewage preparation in oil field
-TBF-I has good viscosity reducing effect, and at conventional concentration 1000～2000mg/L, under 1: 1 the condition of liquid oil ratio, viscosity break ratio can reach more than 95%.And in the progradation of stratum, further mix with formation water, can see well viscosity reducing effect again, final viscosity break ratio can reach 99%;
The TBF-I solution of-1500mg/L and 2000mg/L concentration, viscosity reducing effect is more approaching, and the viscosity reducing effect of 1000mg/L concentration is relatively poor, from practicing thrift the angle of cost, the suggestion field trial is selected the solution of 1500mg/L concentration for use.
-TBF-I extraction liquid gas breakdown of emulsion cruelly under the condition that does not add any demulsifier, and residual solution still contains certain density special TBF-I effective ingredient, can reuse the preparation displacing fluid, reduces production costs at the protection environment.
-TBF-I has good profit Gravity Separation effect in capillary, even oil-sand is soaked, also can see tangible washing oil ability; Explain that the remaining oil that is easy between the reservoir rock hole washes down; Coalescence is taken away together, reaches increase output, improves the purpose of oil recovery.
-through indoor core oil displacement experiment, TBF-I drives and can improve recovery ratio 24%, and ultimate recovery can reach 75%.Compare with ternary composite driving, TBF-I drives and can improve recovery ratio 6%.
The oil displacement efficiency of pilot field test is remarkable, and TBF-I drives and can improve recovery ratio 17.3%, and 9 oral examinations of whole test district are tested oil well day oil production and on average improved and surpass 250%, moisturely drops to 83.5%, has descended 16.5 percentage points.
The preparation of high molecular surfactant TBF-II:
Earlier the water with 1/3V (V is the effective volume of agitated reactor) joins in the agitated reactor that said molecular template is housed, example (1.0: 1.0: 1.0) in molar ratio, add 2-propylene-1-sodium sulfonate, 1-phenylacrylic acid, N-ethyl-(N '; N '-dimethyl-N '-amyl group-(5 '-cyclohexyl) ammonium bromide)-acrylamide; Stirring is dissolved them fully, and with pH value conditioning agent conditioned reaction solution, making its pH is about 5.8 then; Feed nitrogen protection; When being heated to 48 ℃, stirring mixes it, and keeps more than 30 minutes.Then, slowly add the catalyst sodium peroxydisulfate again, reacted about 3.0 hours.
About heat temperature raising to 72 ℃, add pH value conditioning agent, regulating pH is about 11.5, adds initator (ammonium persulfate-sodium sulfite) again, causes copolymerization about 5.0 hours, the reaction end.This product is a TBF-II monobasic functional macromolecule aqueous surfactant solution.After the drying, obtain Powdered TBF-II high molecular polymer.
The mensuration of TBF-II molecular weight:
Press GB12005.1-89 and G/T12005.10-92 national standard, use determination of ubbelohde viscometer.Use polyacrylamide inherent viscosity method determining molecular weight, in the NaCl of the 30 ℃ of following 1mol/L aqueous solution, measure its [η]=18.30mL/g, be calculated as follows its viscosity average molecular weigh M:
M＝802*[η]
1.25＝802*18.30
1.25＝30355。
On the infrared spectrum of TBF-II, can see existence: 3423cm
-1, 1700cm
-1Be the carboxyl characteristic absorption; 3100-3000cm
-1, 1642cm
-1It is the characteristic absorption of C=C key; 2916cm
-1, 2850cm
-1The peak at place is the characteristic absorption of chain alkyl methylene; 3208cm
-1, 1669cm
-1With 1189cm
-1It is the characteristic absorption of amide groups; 1384cm
-1Characteristic absorption for sulfonate; 1600～1430cm
-1Be the phenyl characteristic absorption; 1453cm
-1And 3400cm
-1Corresponding to the nitrogen cation; The existence of these characteristic peaks shows in the molecular structure of target product and has above-mentioned group, comprising: carboxyl, two key, amide groups, sulfonate, nitrogen cation, chain alkyl, phenyl etc.
The laboratory experiment data:
The compatibility experimental data of TBF-II solution and stratum sewage (being the salt-resistance experiment)
In order to realize directly disposing TBF-II solution with oilfield sewage, pollute thereby reduce, the protection environment, thus carried out this compatibility experiment.Adopting the stratum sewage compound concentration of 350000mg/L salinity is the TBF-II solution of 1500mg/L.The TBF-II solution of 1500mg/L concentration under 25 ℃, at 450nm, after placing different time, is measured its absorbance A with spectrophotometer.
| Time (H) | Absorbance (A) | |
| 0 | 1.40 | 0 |
| 24 | 1.42 | 0.02 |
| 48 | 1.45 | 0.05 |
| 72 | 1.42 | 0.02 |
Δ A representes the variation difference that absorbance A increases in time in the last table, and its value is more little, and compatibility is good more.
Result of the test shows, prolongs in time, and big variation does not take place absorbance A, proves absolutely that the stratum sewage of TBF-II and 350000mg/L salinity is compatibility, has good " salt-resistance ".Can realize fully directly with oilfield sewage configuration TBF-II solution.
Sewage and the contrast of distilled water preparation TBF-II solution viscosity stability
The viscosity of TBF-II solution has a strong impact on the TBF-II oil displacement efficiency, so research sewage influences the TBF-II solution viscosity.Elder generation's water is mixed with concentration 5000mg/L mother liquor, uses extraction sewage and distilled water respectively with the TBF-II solution of mother liquor dilution as 1000mg/L and 1200mg/L then.Oxygen free condition is preserved down, regularly under 45 ℃ of conditions, measures viscosity with Brookfield viscometer, compares.
Result of the test shows, can directly prepare TBF-II solution with sewage, and to the not influence of its viscosity.Both practice thrift cost, protected environment again.
Anaerobic bacteria is to the influence of TBF-II
In oilfield sewage, contain a large amount of bacteriums, have very strong bactericidal effect in order to confirm TBF-II, the spy carries out this experiment.
Introduced quaternary ammonium salt monomer in the TBF-II molecular structure, quaternary surfactant has the efficient sterilizing effect to sulfate reducing bacteria, has the antibiont degradation characteristic.
TBF-II body viscosity data
The viscosity of TBF-II solution has decisive influence to the site construction technology flow process of TBF-II, so carry out TBF-II solution body Study on Viscosity.
| TBF concentration mg/ |
500 | 1000 | 1500 | 2000 | 5000 | 10000 | 15000 | 20000 |
| Viscosity mPa.s | 1.75 | 1.88 | 2.13 | 2.25 | 2.45 | 2.58 | 2.59 | 2.58 |
Experimental result explanation: the TBF-II body is under high concentration (20000mg/L), and its viscosity is similar with the viscosity of water, constructs easily, injection technology is simple.
Solution viscosity reduction experimental data table
TBF-II solution is big more to the viscosity reduction ability of crude oil, and oil displacement efficiency is strong more, and this experiment is in order to select suitable TBF-II concentration of aqueous solution, to reach best viscosity reduction and oil displacement efficiency.
Experimental result proves:
-in the mixture of TBF solution and oil, TBF-II concentration is high, and viscosity break ratio is just high;
-in the mixture of TBF solution and oil, the ratio that crude oil accounts for is high, and viscosity reducing effect is just poor; Under 1: 1 situation of liquid oil ratio, viscosity break ratio＞95%;
-along with the prolongation of time, viscosity break ratio changes little, explains that solution has emulsifying capacity and good stability preferably;
The TBF-II viscosity reducing effect of-1000mg/L is poor, and the TBF-II viscosity reducing effect of 1500mg/L and 2000mg/L is similar, considers cost factor, advises the TBF-II solution of on-the-spot guiding experiment selected 1500mg/L concentration
TBF-II type and the contrast of ternary system emulsifying effectiveness
To the emulsifying effectiveness contrast experiment of crude oil, prove that the TBF-II type has efficient solubilising and emulsified crude oil ability than common ternary oil displacement system (alkylbenzene xanthate, oil xanthate etc.) through TBF-II type and ternary system.
The Gravity Separation experiment of profit in capillary
Through the experiment of the crude oil Gravity Separation in the capillary, can prove that TBF-II has stronger permeability, can get into easily in the fine gap of formation rock, and the mother oil displacement in the slit is come out, improve oil displacement efficiency greatly.
When not adding TBF-II in the capillary, less than 4mm pipe gravitational differentiation difficulty, the 5mm pipe can differentiation through agitating.
When adding the TBF-II solution of 1500mg/L in the capillary, float to the top greater than the crude oil in the 2mm capillary on all, after 2 hours, the crude oil in the 1mm capillary almost floats to the top on all.
Sudden and violent gas experiment
In order to confirm whether easily breakdown of emulsion of output liquid, and whether the oil behind the breakdown of emulsion, water two meet related request mutually, and the spy carries out aeration experiment.
The TBF-II aqueous solution of 1500mg/L is mixed with 1: 1,1: 2,1: 3 volume ratio with crude oil, form emulsified solution, this emulsified solution mixes in 1: 2 ratio with formation water, and sudden and violent gas can find out after 4 hours that layering liquid becomes clearly gradually.Crude oil on the glass wall, also wall built-up not gradually.Explain that thinner can form water membrane between crude oil and rock, steel pipe, play good drag reduction washing oil effect.Coalescence is effective, is easy to breaking emulsion and dewatering after the exploitation.
Upper strata after layering oil mensuration is moisture, lower layer of water is measured oil-containing, it is following to record data:
Moisture result sees from oil-containing, the dehydration of this thinner, demulsification reached the oil field with the standard of demulsifier (oil phase is moisture≤30%, water oil-containing≤240mg/L).
Gather and drive under the different recoverys percent of reserves in back TBF-II and drive and improve the recovery ratio effect comparison
For after studying conventional polymer and driving, TBF-II drives the effect that improves recovery ratio, and gathers and drive the influence that recovery percent of reserves is driven TBF-II, hereby experiment.Result such as following table.
| Polyacrylamide drives the back recovery percent of reserves | TBF-II drives the back recovery percent of reserves | TBF-II drives the raising recovery ratio |
| 40.8％ | 59.5％ | 18.7％ |
| 50.3％ | 65.9％ | 15.6％ |
| 56.3％ | 67.9％ | 11.6％ |
The result shows: gather and drive back recovery ratio raising rate＞10% that drives of TBF-II, and gather that to drive the back recovery percent of reserves high more, the amplitude that TBF-II improves recovery ratio is more little.
Embodiment 3
The preparation of high molecular surfactant TBF-III
Earlier the water with 1/3V (V is the effective volume of agitated reactor) joins in the agitated reactor that said molecular template is housed, example (1.0: 1.0: 1.0) in molar ratio again, add 3-phenyl-2-propylene-1-sodium sulfonate, 1-(2 '-mercapto-imidazolyl)-acrylic acid, N-ethyl-(N '; N '-dimethyl-N '-dodecyl-(12 '-carboxylic acid) ammonium)-acrylamide; Stirring is dissolved it fully, and with pH value conditioning agent conditioned reaction solution, making its pH is about 5.3 then; Feed nitrogen protection; When being heated to 48 ℃, stirring mixes it, and keeps more than 30 minutes.Then, slowly add the catalyst potassium peroxydisulfate again, reacted about 3.0 hours.
About heat temperature raising to 70 ℃, add pH value conditioning agent, regulating pH is about 11.5, adds initator (ammonium persulfate-sodium sulfite) again, causes copolymerization about 5.0 hours, the reaction end.This product is a TBF-III monobasic functional macromolecule aqueous surfactant solution.After the drying, obtain Powdered TBF-III high molecular polymer.
The mensuration of TBF-III molecular weight:
Use determination of ubbelohde viscometer by GB 12005.1-89 and G/T12005.10-92.Use polyacrylamide inherent viscosity method determining molecular weight, in the NaCl of the 30 ℃ of following 1mol/L aqueous solution, measure its [η]=28.37mL/g, be calculated as follows its viscosity average molecular weigh M:
M＝802*[η]
1.25＝802*28.37
1.25＝52510
In the infrared spectrum of TBF-III, can see existence: 3420cm
-1, 1702cm
-1Be the carboxyl characteristic absorption; 3100-3000cm
-1, 1646cm
-1It is the characteristic absorption of C=C key; 2912cm
-1, 2858cm
-1The peak at place is the characteristic absorption of chain alkyl methylene; 3201cm
-1, 1669cm
-1With 1189cm
-1It is the characteristic absorption of amide groups; 1385cm
-1Characteristic absorption for sulfonate; 1600～1436cm
-1Be the phenyl characteristic absorption; 2956cm
-1, 1574cm
-1, 1167cm
-1Be the imidazole ring characteristic absorption; 2483cm
-1Be the sulfydryl characteristic absorption; 1452cm
-1And 3408cm
-1Corresponding to the nitrogen cation; The existence of these characteristic peaks shows in the molecular structure of target product and has carboxyl, two key, amide groups, nitrogen cation, chain alkyl, phenyl, sulfydryl, imidazole ring, sulfonate etc.
The compatibility experimental data of TBF-III solution and stratum sewage (being the salt-resistance experiment)
In order to realize directly disposing TBF-III solution with oilfield sewage, pollute thereby reduce, the protection environment, thus carry out this compatibility experiment.Use the stratum sewage of 400000mg/L salinity to be mixed with the TBF-III solution of concentration as 1500mg/L.Under 25 ℃, at 450nm, after placing different time, measure its absorbance A with spectrophotometer.
| Time (H) | Absorbance (A) | |
| 0 | 1.38 | 0 |
| 24 | 1.43 | 0.05 |
| 48 | 1.46 | 0.08 |
| 72 | 1.42 | 0.04 |
Δ A representes the variation difference that absorbance prolongs in time in the table, and its value is more little, and compatibility is good more.
Result of the test shows, the TBF-III solution of 1500mg/L concentration, and absorbance prolongs in time big variation does not take place, and proves absolutely that the stratum sewage of TBF-III and 400000mg/L salinity is compatibility, has good " salt-resistance ".Can realize fully directly with oilfield sewage configuration TBF-III solution.
Sewage and the contrast of distilled water preparation TBF-III solution viscosity stability
The viscosity of TBF-III solution has a strong impact on the TBF-III oil displacement efficiency, so research sewage influences the TBF-III solution viscosity.Elder generation's water is mixed with concentration 5000mg/L mother liquor, uses extraction sewage and distilled water respectively with the TBF-III solution of mother liquor dilution as 1000mg/L and 1200mg/L then.Oxygen free condition is preserved down, regularly under 45 ℃ of conditions, measures viscosity with Brookfield viscometer, compares.
Result of the test shows, can directly prepare TBF-III solution with sewage, and to the not influence of its viscosity.Both practice thrift cost, protected environment again.
Anaerobic bacteria is to the influence of TBF-III
In oilfield sewage, contain a large amount of bacteriums, have very strong bactericidal effect in order to confirm TBF-III, the spy carries out this experiment.
Because introduced quaternary ammonium salt monomer unit, nitrogenous sulfhydryl heterocycle in the TBF-III molecular structure, it has the efficient sterilizing effect to sulfate reducing bacteria, has the antibiont degradation characteristic.
The body viscosity data
The viscosity of TBF-III solution has decisive influence to the site construction technology flow process of TBF-III, so carry out TBF-III solution body Study on Viscosity.
| TBF concentration mg/ |
500 | 1000 | 1500 | 2000 | 5000 | 10000 | 15000 | 20000 |
| Viscosity mPa.s | 1.55 | 1.60 | 1.71 | 1.89 | 2.24 | 2.55 | 2.58 | 2.57 |
Description of test: the TBF-III body is under high concentration (20000mg/L), and its viscosity is similar with the viscosity of water, and easily construction, injection technology are simple.
TBF-III solution viscosity reduction experimental data table
TBF-III solution is big more to the viscosity reduction ability of crude oil, and oil displacement efficiency is strong more, and this experiment is in order to select suitable TBF-III concentration of aqueous solution, to reach best viscosity reduction and oil displacement efficiency.
Experimental result proves:
-at the mixture of TBF solution with oil, TBF-III concentration is high, and viscosity break ratio is just high;
-at the mixture of TBF solution with oil, the ratio that crude oil accounts for is high, and viscosity reducing effect is just poor; Under 1: 1 situation of liquid oil ratio, viscosity break ratio＞95%;
-along with the prolongation of time, viscosity break ratio changes little, explains that solution has emulsifying capacity and good stability preferably;
The TBF-III viscosity reducing effect of-1000mg/L is poor, and the TBF-III viscosity reducing effect of 1500mg/L and 2000mg/L is similar, considers cost factor, advises the TBF-III solution of on-the-spot guiding experiment selected 1500mg/L concentration.
TBF-III type and the contrast of ternary system emulsifying effectiveness
To the emulsifying effectiveness contrast experiment of crude oil, prove that the TBF-III type has efficient solubilising and emulsified crude oil ability than common ternary oil displacement system (alkylbenzene xanthate, oil xanthate etc.) through TBF-III type and ternary system.
The Gravity Separation experiment of profit in capillary
Through the experiment of the crude oil Gravity Separation in the capillary, can prove that TBF-III has stronger permeability, can get into easily in the fine gap of formation rock, and the mother oil displacement in the slit is come out, improve oil displacement efficiency greatly.
When not adding TBF-III in the capillary, less than 4mm pipe gravitational differentiation difficulty, the 5mm pipe can differentiation through agitating.
When adding the TBF-III solution of 1500mg/L in the capillary, float to the top greater than the crude oil in the 2mm capillary on all, after 2 hours, the crude oil in the 1mm capillary almost floats to the top on all.
Sudden and violent gas experiment
In order to confirm whether easily breakdown of emulsion of output liquid, and whether the oil behind the breakdown of emulsion, water two meet related request mutually, and the spy carries out aeration experiment.
The TBF-III aqueous solution of 1500mg/L is mixed with 1: 1,1: 2,1: 3 volume ratio with crude oil, form emulsified solution, this emulsified solution mixes in 1: 2 ratio with formation water, and sudden and violent gas can find out after 4 hours that layering liquid becomes clearly gradually.Crude oil on the glass wall, also wall built-up not gradually.Explain that thinner can form water membrane between crude oil and rock, steel pipe, play good drag reduction washing oil effect.Coalescence is effective, is easy to breaking emulsion and dewatering after the exploitation.
Upper strata after layering oil mensuration is moisture, lower layer of water is measured oil-containing, it is following to record data:
Moisture result sees from oil-containing, the dehydration of this thinner, demulsification reached the oil field with the standard of demulsifier (oil phase is moisture≤30%, water oil-containing≤240mg/L).
Gather and drive under the different recoverys percent of reserves in back TBF-III and drive and improve the recovery ratio effect comparison
For after studying conventional polymer and driving, TBF-III drives the effect that improves recovery ratio, and gathers and drive the influence that recovery percent of reserves is driven TBF, hereby experiment.
| Polyacrylamide drives the back recovery percent of reserves | TBF-III drives the back recovery percent of reserves | TBF-III drives the raising recovery ratio |
| 35.9％ | 56.5％ | 20.6％ |
| 44.3％ | 62.6％ | 18.3％ |
| 58.3％ | 68.5％ | 10.2％ |
The result shows: gather drive the back TBF-III drive raising recovery ratio＞10%, and gather drive the back recovery percent of reserves high more, the amplitude that TBF-III further improves recovery ratio is more little.
Embodiment 4
The preparation of high molecular surfactant TBF-IV
Earlier the water with 1/3V (V is the effective volume of agitated reactor) joins in the agitated reactor that said molecular template is housed, example (1.0: 1.0: 1.0) in molar ratio, add 2-propylene-1-sodium sulfonate, 1-(2 '-mercapto-imidazolyl)-acrylic acid, N-ethyl-(N '; N '-dimethyl-N '-undecyl-(11 '-carboxylic acid) ammonium)-acrylamide; Stirring is dissolved them fully, and with pH value conditioning agent conditioned reaction solution, making its pH is about 5.2 then; Feed nitrogen protection; When being heated to 45 ℃, stirring mixes it, and keeps more than 30 minutes.Then, slowly add the catalyst sodium peroxydisulfate again, reacted about 3.0 hours.
About heat temperature raising to 68 ℃, add pH value conditioning agent, regulating pH is about 11.6, adds initator (ammonium persulfate-sodium sulfite) again, causes copolymerization about 5.0 hours, the reaction end.This product is a TBF-IV monobasic functional macromolecule aqueous surfactant solution.Through super-dry, obtain Powdered TBF-IV high molecular polymer.
The mensuration of TBF-IV molecular weight:
Press GB 12005.1-89 and G/T12005.10-92 national standard, use determination of ubbelohde viscometer.Use polyacrylamide inherent viscosity method determining molecular weight, in the NaCl of the 30 ℃ of following 1mol/L aqueous solution, measure its [η]=30.67mL/g, be calculated as follows its viscosity average molecular weigh M:
M＝802*[η]
1.25＝802*30.67
1.25＝57885
From the infrared spectrum of TBF-IV, can see: 3420cm
-1, 1710cm
-1About be the carboxyl characteristic absorption; 3100-3000cm
-1, 1645cm
-1It is the characteristic absorption of C=C key; 2911cm
-1, 2855cm
-1The peak at place is the characteristic absorption of chain alkyl methylene; 3200cm
-1, 1666cm
-1With 1190cm
-1It is the characteristic absorption of amide groups; 1383cm
-1Characteristic absorption for sulfonate; 2958cm
-1, 1570cm
-1, 1168cm
-1Be the imidazole ring characteristic absorption; 2485cm
-1Be the sulfydryl characteristic absorption; 1454cm
-1And 3402cm
-1Corresponding to the nitrogen cation; The existence of these characteristic peaks shows groups such as having two keys, amide groups, nitrogen cation, chain alkyl, carboxyl, sulfonate, sulfydryl, imidazole ring in the molecular structure of target product.
The compatibility experimental data of TBF-IV solution and stratum sewage (being the salt-resistance experiment)
In order to realize directly disposing TBF-IV solution with oilfield sewage, pollute thereby reduce, the protection environment, thus carry out this compatibility experiment.Be mixed with the TBF-IV solution of 1500mg/L with the stratum sewage of 400000mg/L salinity.Under 25 ℃, at 450nm, after placing different time, measure its absorbance A with spectrophotometer.
| Time (H) | Absorbance (A) | |
| 0 | 1.39 | 0 |
| 24 | 1.44 | 0.05 |
| 48 | 1.41 | 0.02 |
| 72 | 1.43 | 0.04 |
Δ A representes the variation difference that absorbance A prolongs in time in the last table, and its value is more little, and compatibility is good more.
Result of the test shows, the TBF-IV solution of 1500mg/L concentration, and absorbance A prolongs in time big variation does not take place, and proves absolutely that the stratum sewage of TBF-IV and 400000mg/L salinity is compatibility, has good " salt-resistance ".Can realize fully directly with oilfield sewage configuration TBF-IV solution.
Sewage and the contrast of distilled water preparation TBF-IV solution viscosity stability
The viscosity of TBF-IV solution has a strong impact on the TBF-IV oil displacement efficiency, so research sewage influences the TBF-IV solution viscosity.Elder generation's water is mixed with concentration 5000mg/L mother liquor, uses extraction sewage and distilled water respectively with the TBF-IV solution of mother liquor dilution as 1000mg/L and 1200mg/L then.Oxygen free condition is preserved down, regularly under 45 ℃ of conditions, measures viscosity with Brookfield viscometer, compares.
Result of the test shows, can directly prepare TBF-IV solution with sewage, and to the not influence of its viscosity.Both practice thrift cost, protected environment again.
Influence detects data to anaerobic bacteria to TBF-IV
In oilfield sewage, contain a large amount of bacteriums, have very strong bactericidal effect in order to confirm TBF-IV, the spy carries out this experiment.
Introduced quaternary ammonium salt, nitrogenous sulfhydryl heterocycle in the TBF-IV molecular structure, it has the efficient sterilizing effect to sulfate reducing bacteria, has the antibiont degradation characteristic.
TBF-IV body viscosity data
The viscosity of TBF-IV solution has decisive influence to the site construction technology flow process of TBF-IV, so carry out TBF-IV solution body Study on Viscosity.
| TBF concentration mg/ |
500 | 1000 | 1500 | 2000 | 5000 | 10000 | 15000 | 20000 |
| Viscosity mPa.s | 1.57 | 1.63 | 1.69 | 1.80 | 2.21 | 2.51 | 2.55 | 2.58 |
Description of test: the TBF-IV body is under high concentration (20000mg/L), and its viscosity is similar with the viscosity of water, and easily construction, injection technology are simple.
TBF-IV solution viscosity reduction experimental data table
TBF-IV solution is big more to the viscosity reduction ability of crude oil, and oil displacement efficiency is strong more, and this experiment is in order to screen suitable TBF-IV concentration of aqueous solution, to reach best viscosity reduction and oil displacement efficiency.
The experiment proof:
-at the mixture of TBF solution with oil, TBF-IV concentration is high, and viscosity break ratio is just high;
-at the mixture of TBF solution with oil, the ratio that crude oil accounts for is high, and viscosity reducing effect is just poor; Under 1: 1 situation of liquid oil ratio, viscosity break ratio＞95%;
-along with the prolongation of time, viscosity break ratio changes little, explains that solution has emulsifying capacity and good stability preferably;
The TBF-IV viscosity reducing effect of-1000mg/L is poor, and the TBF-IV viscosity reducing effect of 1500mg/L and 2000mg/L is similar, considers cost factor, advises the TBF-IV solution of on-the-spot guiding experiment selected 1500mg/L concentration.
TBF-IV type and the contrast of ternary system emulsifying effectiveness
To the emulsifying effectiveness contrast experiment of crude oil, prove that the TBF-IV type has efficient solubilising and emulsified crude oil ability than common ternary oil displacement system (alkylbenzene xanthate, oil xanthate etc.) through TBF-IV type and ternary system.
The Gravity Separation experiment of profit in capillary
Through the experiment of the crude oil Gravity Separation in the capillary, can prove that TBF-IV has stronger permeability, can get into easily in the fine gap of formation rock, and the mother oil displacement in the slit is come out, improve oil displacement efficiency greatly.
When not adding TBF-IV in the capillary, less than 4mm pipe gravitational differentiation difficulty, the 5mm pipe can differentiation through agitating.
When adding the TBF-IV solution of 1500mg/L in the capillary, float to the top greater than the crude oil in the 2mm capillary on all, after 2 hours, the crude oil in the 1mm capillary almost floats to the top on all.
Sudden and violent gas experiment
In order to confirm whether easily breakdown of emulsion of output liquid, and whether the oil behind the breakdown of emulsion, water two meet related request mutually, and the spy carries out aeration experiment.
The TBF-IV aqueous solution of 1500mg/L is mixed with 1: 1,1: 2,1: 3 volume ratio with crude oil, form emulsified solution, this emulsified solution mixes in 1: 2 ratio with formation water, and sudden and violent gas can find out after 4 hours that layering liquid becomes clearly gradually.Crude oil on the glass wall, also wall built-up not gradually.Explain that thinner can form water membrane between crude oil and rock, steel pipe, play good drag reduction washing oil effect.Coalescence is effective, is easy to breaking emulsion and dewatering after the exploitation.
Upper strata after layering oil mensuration is moisture, lower layer of water is measured oil-containing, it is following to record data:
Moisture result sees from oil-containing, the dehydration of this thinner, demulsification reached the oil field with the standard of demulsifier (oil phase is moisture≤30%, water oil-containing≤240mg/L).
Gather and drive under the different recoverys percent of reserves in back TBF-IV and drive and improve the recovery ratio effect comparison
For after studying conventional polymer and driving, TBF-IV drives the effect that improves recovery ratio, and gathers and drive the influence that recovery percent of reserves is driven TBF-IV, hereby experiment.
| Polyacrylamide drives the back recovery percent of reserves | TBF-IV drives the back recovery percent of reserves | TBF-IV drives the raising recovery ratio |
| 22.3％ | 60.9％ | 38.6％ |
| 48.7％ | 66.3％ | 17.6％ |
| 55.7％ | 68.2％ | 12.5％ |
The result shows: gather drive the back TBF-IV drive raising recovery ratio＞10%, and gather drive the back recovery percent of reserves high more, the amplitude that TBF-IV further improves recovery ratio is more little.
Embodiment 5
The preparation of TBF-V high molecular surfactant
Earlier the water with 1/3V (V is the effective volume of agitated reactor) joins in the agitated reactor that said molecular template is housed, example (1.0: 1.0: 1.0) in molar ratio again, add 3-(4 '-sulfonic group-phenyl)-2-propylene-1-sodium sulfonate, 1-(2 '-mercapto-imidazolyl)-acrylic acid, N-ethyl-(N '; N '-dimethyl-N '-dodecyl-(12 '-sulfonic acid) ammonium)-acrylamide; Stirring is dissolved it fully, and with pH value conditioning agent conditioned reaction solution, making its pH is about 5.0 then; Feed nitrogen protection; When being heated to 49 ℃, stirring mixes it, and keeps more than 30 minutes.Then, slowly add the catalyst ammonium persulfate again, reacted about 3.0 hours.
About heat temperature raising to 65 ℃, add pH value conditioning agent, regulating pH is about 11.0, adds initator (ammonium persulfate-sodium sulfite) again, causes copolymerization about 5.0 hours, the reaction end.This product is a TBF-V monobasic functional macromolecule aqueous surfactant solution.After the drying, obtain pulverous pure TBF-V high molecular polymer.
The mensuration of TBF-V molecular weight:
Press GB 12005.1-89 and G/T12005.10-92 national standard, use determination of ubbelohde viscometer.Use polyacrylamide inherent viscosity method determining molecular weight, in the NaCl of the 30 ℃ of following 1mol/L aqueous solution, measure its [η]=21.68mL/g, be calculated as follows its viscosity average molecular weigh M:
M＝802*[η]
1.25＝802*21.68
1.25＝37518
From the infrared spectrum of TBF-V, can see: 3418cm
-1, 1712cm
-1Be the carboxyl characteristic absorption; 3100-3000cm
-1, 1640cm
-1It is the characteristic absorption of C=C key; 2911cm
-1, 2852cm
-1The peak at place is the characteristic absorption of chain alkyl methylene; 3204cm
-1, 1667cm
-1With 1190cm
-1About be the characteristic absorption of amide groups; 1387cm
-1About be the characteristic absorption of sulfonate; 1600～1450cm
-1Be the phenyl characteristic absorption; 2958cm
-1, 1576cm
-1, 1165cm
-1Be the imidazole ring characteristic absorption; 2485cm
-1Be the sulfydryl characteristic absorption; 1457cm
-1And 3400cm
-1Corresponding to the nitrogen cation; The existence of these characteristic peaks shows and has two keys, amide groups, nitrogen cation, chain alkyl, sulfydryl, benzene sulfonate in the molecular structure of target product.
The laboratory experiment data
The compatibility experimental data of TBF-V solution and stratum sewage (being the salt-resistance experiment)
In order to realize directly disposing TBF-V solution with oilfield sewage, pollute thereby reduce, the protection environment, thus carry out this compatibility experiment.Be mixed with the TBF-V solution of 1500mg/L with the stratum sewage of 350000mg/L salinity.Under 25 ℃, at 450nm, after placing different time, measure its absorbance A with spectrophotometer.
| Time (H) | Absorbance (A) | |
| 0 | 1.38 | 0 |
| 24 | 1.40 | 0.02 |
| 48 | 1.41 | 0.03 |
| 72 | 1.40 | 0.00 |
Δ A representes the poor of absorbance in the table, and its value is more little, and compatibility is good more.
Result of the test shows, the TBF-V solution absorbency of 1500mg/L concentration prolongs in time big variation does not take place, and proves absolutely that the stratum sewage of TBF-V and 350000mg/L salinity is compatibility, has good " salt-resistance ".Can realize fully directly with oilfield sewage configuration TBF-V solution.
Sewage and the contrast of distilled water preparation TBF-V solution viscosity stability
The viscosity of TBF-V solution has a strong impact on the TBF-V oil displacement efficiency, so research sewage influences the TBF-V solution viscosity.Elder generation's water is mixed with concentration 5000mg/L mother liquor, uses extraction sewage and distilled water respectively with the TBF-V solution of mother liquor dilution as 1000mg/L and 1200mg/L then.Oxygen free condition is preserved down, regularly under 45 ℃ of conditions, measures viscosity with Brookfield viscometer, compares.
Result of the test shows, can directly prepare TBF-V solution with sewage, and to the not influence of its viscosity.Both practice thrift cost, protected environment again.
Influence detects data to anaerobic bacteria to TBF-V
In oilfield sewage, contain a large amount of bacteriums, have very strong bactericidal effect in order to confirm TBF-V, the spy carries out this experiment.
Introduced quaternary ammonium salt monomer, imidazole radicals in the TBF-V molecular structure, it has the efficient sterilizing effect to sulfate reducing bacteria, has the antibiont degradation characteristic.
TBF-V body viscosity data
The viscosity of TBF-V solution has decisive influence to the site construction technology flow process of TBF-V, so carry out TBF-V solution body Study on Viscosity.
| TBF concentration mg/ |
500 | 1000 | 1500 | 2000 | 5000 | 10000 | 15000 | 20000 |
| Viscosity mPa.s | 1.07 | 1.68 | 1.75 | 1.82 | 2.11 | 2.31 | 2.35 | 2.32 |
Description of test: the TBF-V body is under high concentration (20000mg/L), and its viscosity is similar with the viscosity of water, and easily construction, injection technology are simple.
TBF-V solution viscosity reduction experimental data table
TBF-V solution is big more to the viscosity reduction ability of crude oil, and oil displacement efficiency is strong more, and this experiment is in order to screen suitable TBF-V concentration of aqueous solution, to reach best viscosity reduction and oil displacement efficiency.
Experimental result proves:
-at the mixture of TBF solution with oil, TBF-V concentration is high, and viscosity break ratio is just high;
-at the mixture of TBF solution with oil, the ratio that crude oil accounts for is high, and viscosity reducing effect is just poor; Under 1: 1 situation of liquid oil ratio, viscosity break ratio＞95%;
-along with the prolongation of time, viscosity break ratio changes little, explains that solution has emulsifying capacity and good stability preferably;
The TBF-V viscosity reducing effect of-1000mg/L is poor, and the TBF-V viscosity reducing effect of 1500mg/L and 2000mg/L is similar, considers cost factor, advises the TBF-V solution of on-the-spot guiding experiment selected 1500mg/L concentration.
TBF-V type and the contrast of ternary system emulsifying effectiveness
Through TBF-V type and ternary system emulsifying effectiveness contrast experiment, prove that the TBF-V type has better efficient solubilising and emulsified crude oil ability than common ternary oil displacement system (alkylbenzene xanthate, oil xanthate etc.) to crude oil.
The Gravity Separation experiment of profit in capillary
Through the experiment of the crude oil Gravity Separation in the capillary, can prove that TBF-V has stronger permeability, can get into easily in the fine gap of formation rock, and the mother oil displacement in the slit is come out, improve oil displacement efficiency greatly.
When not adding TBF-V in the capillary, less than 4mm pipe gravitational differentiation difficulty, the 5mm pipe can differentiation through agitating.
When adding the TBF-V solution of 1500mg/L in the capillary, float to the top greater than the crude oil in the 2mm capillary on all, after 2 hours, the crude oil in the 1mm capillary almost floats to the top on all.
Sudden and violent gas experiment
In order to confirm whether easily breakdown of emulsion of output liquid, and whether the oil behind the breakdown of emulsion, water two meet related request mutually, and the spy carries out aeration experiment.
The TBF-V aqueous solution of 1500mg/L is mixed with 1: 1,1: 2,1: 3 volume ratio with crude oil, form emulsified solution, this emulsified solution mixes in 1: 2 ratio with formation water, and sudden and violent gas can find out after 4 hours that layering liquid becomes clearly gradually.Crude oil on the glass wall, also wall built-up not gradually.Explain that thinner can form water membrane between crude oil and rock, steel pipe, play good drag reduction washing oil effect.Coalescence is effective, is easy to breaking emulsion and dewatering after the exploitation.
Upper strata after layering oil mensuration is moisture, lower layer of water is measured oil-containing, it is following to record data:
Moisture result sees from oil-containing, the dehydration of this thinner, demulsification reached the oil field with the standard of demulsifier (oil phase is moisture≤30%, water oil-containing≤240mg/L).
Gather and drive under the different recoverys percent of reserves in back TBF and drive and improve the recovery ratio effect comparison
For after studying conventional polymer and driving, TBF-V drives the effect that improves recovery ratio, and gathers and drive the influence that recovery percent of reserves is driven TBF-V, hereby experiment.
| Polyacrylamide drives the back recovery percent of reserves | TBF-V drives the back recovery percent of reserves | TBF-V drives the raising recovery ratio |
| 32.3％ | 66.4％ | 34.1％ |
| 47.3％ | 69.8％ | 22.5％ |
| 55.6％ | 70.2％ | 14.6％ |
The result shows: polyacrylamide drive the back TBF-V drive raising recovery ratio＞10%, and polyacrylamide drive the back recovery percent of reserves high more, the amplitude that TBF-V further improves recovery ratio is more little.
The preparation of TBF-VI:
Earlier the water with 1/3V (V is the effective volume of agitated reactor) joins in the agitated reactor that said molecular template is housed, example (1.0: 1.0: 1.0) in molar ratio again, add 3-(4 '-sulfonic group-phenyl)-2-propylene-1-sodium sulfonate, 1-imidazole radicals-acrylic acid, N-ethyl-(N '; N '-dimethyl-N '-dodecyl-(12 '-sulfonic acid) ammonium)-acrylamide; Stirring is dissolved it fully, and with pH value conditioning agent conditioned reaction solution, making its pH is about 6.0 then; Feed nitrogen protection; When being heated to 42 ℃, stirring mixes it, and keeps more than 30 minutes.Then, slowly add the catalyst potassium peroxydisulfate again, reacted about 3.0 hours.
About heat temperature raising to 60 ℃, add pH value conditioning agent, regulating pH is about 11.2, adds initator (ammonium persulfate-sodium sulfite) again, causes copolymerization about 5.0 hours, the reaction end.This product is a TBF-V monobasic functional macromolecule aqueous surfactant solution.After the drying, obtain pulverous pure TBF-V high molecular polymer.
The mensuration of TBF-VI molecular weight:
Use determination of ubbelohde viscometer by GB 12005.1-89 and G/T12005.10-92 national standard.Use polyacrylamide inherent viscosity method determining molecular weight, in the NaCl of the 30 ℃ of following 1mol/L aqueous solution, measure its [η]=19.38mL/g, be calculated as follows its viscosity average molecular weigh M:
M＝802*[η]
1.25＝802*19.38
1.25＝32?611
From the infrared spectrum of TBF-VI, can find out: 3418cm
-1, 1705cm
-1Be the carboxyl characteristic absorption; 3100-3000cm
-1, 1640cm
-1It is the characteristic absorption of C=C key; 2909cm
-1, 2850cm
-1The peak at place is the characteristic absorption of chain alkyl methylene; 3201cm
-1, 1665cm
-1With 1188cm
-1About be the characteristic absorption of amide groups; 1385cm
-1About be the characteristic absorption of sulfonate; 1600～1430cm
-1Be the phenyl characteristic absorption; 2952cm
-1, 1571cm
-1, 1165cm
-1Be the imidazole ring characteristic absorption; 1452cm
-1And 3400cm
-1Corresponding to the nitrogen cation; The existence of these characteristic peaks shows and has (benzene sulfonate and sulfonic absworption peak positions) such as two keys, amide groups, nitrogen cation, chain alkyl, sulfonate, carboxyl, imidazole ring, phenyl in the molecular structure of target product.
The laboratory experiment data:
The compatibility experimental data of TBF-VI solution and stratum sewage (being the salt-resistance experiment)
In order to realize directly disposing TBF-VI solution with oilfield sewage, pollute thereby reduce, the protection environment, thus carry out this compatibility experiment.Be mixed with the TBF-VI solution of 1500mg/L with the stratum sewage of 400000mg/L salinity.Under 25 ℃, at 450nm, after placing different time, measure its absorbance A with spectrophotometer.
| Time (H) | Absorbance (A) | |
| 0 | 1.41 | 0 |
| 24 | 1.43 | 0.02 |
| 48 | 1.40 | -0.01 |
| 72 | 1.42 | 0.01 |
Δ A in the table representes the variation difference that absorbance prolongs in time, and its value is more little, and compatibility is good more.
Result of the test shows, the TBF-VI solution of 1500mg/L concentration, and its absorbance prolongs in time big variation does not take place, and proves absolutely that the stratum sewage of TBF-VI and 400000mg/L salinity is compatibility, has good " salt-resistance ".Can realize fully directly with oilfield sewage configuration TBF-VI solution.
Sewage and the contrast of distilled water preparation TBF-VI solution viscosity stability
The viscosity of TBF-VI solution has a strong impact on the TBF-VI oil displacement efficiency, so research sewage influences the TBF-VI solution viscosity.Elder generation's water is mixed with concentration 5000mg/L mother liquor, uses extraction sewage and distilled water respectively with the TBF-VI solution of mother liquor dilution as 1000mg/L and 1200mg/L then.Oxygen free condition is preserved down, regularly under 45 ℃ of conditions, measures viscosity with Brookfield viscometer, compares.
Result of the test shows, can directly prepare TBF-VI solution with sewage, and to the not influence of its viscosity.Both practice thrift cost, protected environment again.
Influence detects data to anaerobic bacteria to TBF-VI
In oilfield sewage, contain a large amount of bacteriums, have very strong bactericidal effect in order to confirm TBF-VI, the spy carries out this experiment.
Introduced quaternary ammonium salt monomer, imidazole radicals in the TBF-VI molecular structure, it has the efficient sterilizing effect to sulfate reducing bacteria, has the antibiont degradation characteristic.
TBF-VI body viscosity data
The viscosity of TBF-VI solution has decisive influence to the site construction technology flow process of TBF-VI, so carry out TBF-VI solution body Study on Viscosity.
| TBF concentration mg/ |
500 | 1000 | 1500 | 2000 | 5000 | 10000 | 15000 | 20000 |
| Viscosity mPa.s | 1.12 | 1.61 | 1.72 | 1.80 | 2.01 | 2.28 | 2.31 | 2.30 |
Description of test TBF-VI body is under high concentration (20000mg/L), and its viscosity is similar with the viscosity of water, and easily construction, injection technology are simple.
TBF-VI solution viscosity reduction experimental data table
TBF-VI solution is big more to the viscosity reduction ability of crude oil, and oil displacement efficiency is strong more, and this experiment is to select suitable TBF-VI concentration of aqueous solution in order to screen, to reach best viscosity reduction and oil displacement efficiency.
The experiment proof:
-at the mixture of TBF solution with oil, TBF-VI concentration is high, and viscosity break ratio is just high;
-at the mixture of TBF solution with oil, the ratio that crude oil accounts for is high, and viscosity reducing effect is just poor; Under 1: 1 situation of liquid oil ratio, viscosity break ratio＞95%;
-along with the prolongation of time, viscosity break ratio changes little, explains that solution has emulsifying capacity and good stability preferably;
The TBF-VI viscosity reducing effect of-1000mg/L is poor, and the TBF-VI viscosity reducing effect of 1500mg/L and 2000mg/L is similar, considers cost factor, advises the TBF-VI solution of on-the-spot guiding experiment selected 1500mg/L concentration.
TBF-VI type and the contrast of ternary system emulsifying effectiveness
To the emulsifying effectiveness contrast experiment of crude oil, prove that the TBF-VI type has efficient solubilising and emulsified crude oil ability than common ternary oil displacement system (alkylbenzene xanthate, oil xanthate etc.) through TBF-VI type and ternary system.
The Gravity Separation experiment of profit in capillary
Through the experiment of the crude oil Gravity Separation in the capillary, can prove that TBF-VI has stronger permeability, can get into easily in the fine gap of formation rock, and the mother oil displacement in the slit is come out, improve oil displacement efficiency greatly.
When not adding TBF-VI in the capillary, less than 4mm pipe gravitational differentiation difficulty, the 5mm pipe can differentiation through agitating.
When adding the TBF-VI solution of 1500mg/L in the capillary, float to the top greater than the crude oil in the 2mm capillary on all, after 2 hours, the crude oil in the 1mm capillary almost floats to the top on all.
Sudden and violent gas experiment
In order to confirm whether easily breakdown of emulsion of output liquid, and whether the oil behind the breakdown of emulsion, water two meet related request mutually, and the spy carries out aeration experiment.
The TBF-VI aqueous solution of 1500mg/L is mixed with 1: 1,1: 2,1: 3 volume ratio with crude oil, form emulsified solution, this emulsified solution mixes in 1: 2 ratio with formation water, and sudden and violent gas can find out after 4 hours that layering liquid becomes clearly gradually.Crude oil on the glass wall, also wall built-up not gradually.Explain that thinner can form water membrane between crude oil and rock, steel pipe, play good drag reduction washing oil effect.Coalescence is effective, is easy to breaking emulsion and dewatering after the exploitation.
Upper strata after layering oil mensuration is moisture, lower layer of water is measured oil-containing, it is following to record data:
Moisture result sees from oil-containing, the dehydration of this thinner, demulsification reached the oil field with the standard of demulsifier (oil phase is moisture≤30%, water oil-containing≤240mg/L).
Gather and drive under the different recoverys percent of reserves in back TBF-VI and drive and improve the recovery ratio effect comparison
For after studying conventional polymer and driving, TBF-VI drives the effect that improves recovery ratio, and gathers and drive the influence that recovery percent of reserves is driven TBF-VI, hereby experiment.
| Polyacrylamide drives the back recovery percent of reserves | TBF-VI drives the back recovery percent of reserves | TBF-VI drives the raising recovery ratio |
| 26.1％ | 67.6％ | 41.5％ |
| 45.9％ | 68.1％ | 22.2％ |
| 57.0％ | 70.2％ | 13.2％ |
The result shows: gather drive the back TBF-VI drive raising recovery ratio＞10%, and gather drive the back recovery percent of reserves high more, the amplitude that TBF-VI further improves recovery ratio is more little.
Embodiment 7
TBF-VII's is synthetic
Water with 1/3V (V is the effective volume of agitated reactor) joins in the agitated reactor that said molecular template is housed earlier; Add 2-propylene-1-sodium sulfonate, 1-thienyl acrylic acid, N-ethyl-(N ', N '-dimethyl-N '-dodecyl-(12 '-pyrrole radicals) ammonium bromide)-acrylamide example (1.0: 1.0: 1.0) in molar ratio again, stir it is dissolved fully; Then with pH value conditioning agent conditioned reaction solution; Making its pH is about 6.0, feeds nitrogen protection, when being heated to 47 ℃; Stirring mixes it, and keeps more than 30 minutes.Then, slowly add the catalyst potassium peroxydisulfate again, reacted about 3.0 hours.
About heat temperature raising to 65 ℃, add pH value conditioning agent, regulating pH is about 11.5, adds initator (ammonium persulfate-sodium sulfite) again, causes copolymerization about 5.0 hours, the reaction end.This product is a TBF-VII monobasic functional macromolecule aqueous surfactant solution.After the drying, obtain pulverous pure TBF-VII product.
The mensuration of TBF-VII molecular weight:
Press GB 12005.1-89 and G/T12005.10-92 national standard, use determination of ubbelohde viscometer.Use polyacrylamide inherent viscosity method determining molecular weight, in the NaCl of the 30 ℃ of following 1mol/L aqueous solution, measure its [η]=29.39mL/g, be calculated as follows its viscosity average molecular weigh M:
M＝802*[η]
1.25＝802*29.39
1.25＝54881。
From the infrared spectrum of TBF-VII, can see: 3420cm
-1, 1704cm
-1Be the carboxyl characteristic absorption; 3100-3000cm
-1, 1642cm
-1It is the characteristic absorption of C=C key; 2903cm
-1, 2851cm
-1The peak at place is the characteristic absorption of chain alkyl methylene; 3200cm
-1, 1668cm
-1With 1190cm
-1It is the characteristic absorption of amide groups; 1384cm
-1Characteristic absorption for sulfonate; 1600cm
-1, 1486cm
-1, 769cm
-1Be the thienyl characteristic absorption; 1560cm
-1, 1480cm
-1, 1310cm
-1, 1190cm
-1Be the pyrrole radicals characteristic absorption; 1451cm
-1And 3400cm
-1Corresponding to the nitrogen cation; The existence of these characteristic peaks shows and has two keys, amide groups, nitrogen cation, chain alkyl, thienyl, pyrrole radicals, sulfonate etc. in the molecular structure of target product.
The laboratory experiment data:
The compatibility experimental data of TBF-VII solution and stratum sewage (being the salt-resistance experiment)
In order to realize directly disposing TBF-VII solution with oilfield sewage, pollute thereby reduce, the protection environment, thus carry out this compatibility experiment.Be mixed with the TBF-VII solution of 1500mg/L with the stratum sewage of 380000mg/L salinity.Under 25 ℃, at 450nm, after placing different time, measure its absorbance A with spectrophotometer.
| Time (H) | Absorbance (A) | |
| 0 | 1.39 | 0 |
| 24 | 1.43 | 0.04 |
| 48 | 1.43 | 0.04 |
| 72 | 1.42 | 0.03 |
Δ A representes the variation difference that absorbance prolongs in time in the table.Its value is more little, and compatibility is good more.
Result of the test shows, the TBF-VII solution of 1500mg/L concentration, and big variation does not take place in absorbance, proves absolutely that the stratum sewage of TBF-VII and 380000mg/L salinity is compatibility, has good " salt-resistance ".Can realize fully directly with oilfield sewage configuration TBF-VII solution.
Sewage and the contrast of distilled water preparation TBF-VII solution viscosity stability
The viscosity of TBF-VII solution has a strong impact on the TBF-VII oil displacement efficiency, so research sewage influences the TBF-VII solution viscosity.Elder generation's water is mixed with concentration 5000mg/L mother liquor, uses extraction sewage and distilled water respectively with the TBF-VII solution of mother liquor dilution as 1000mg/L and 1200mg/L then.Oxygen free condition is preserved down, regularly under 45 ℃ of conditions, measures viscosity with Brookfield viscometer, compares.
Result of the test shows, can directly prepare TBF-VII solution with sewage, and to the not influence of its viscosity.Both practice thrift cost, protected environment again.
Influence detects data to anaerobic bacteria to TBF-VII
In oilfield sewage, contain a large amount of bacteriums, have very strong bactericidal effect in order to confirm TBF-VII, the spy carries out this experiment.
Introduced quaternary ammonium salt monomer, thienyl in the TBF-VII molecular structure, it has the efficient sterilizing effect to sulfate reducing bacteria, has the antibiont degradation characteristic.
TBF-VII body viscosity data
The viscosity of TBF-VII solution has decisive influence to the site construction technology flow process of TBF-VII, so carry out TBF-VII solution body Study on Viscosity.
| TBF concentration mg/ |
500 | 1000 | 1500 | 2000 | 5000 | 10000 | 15000 | 20000 |
| Viscosity mPa.s | 1.15 | 1.59 | 1.70 | 1.78 | 2.12 | 2.20 | 2.28 | 2.26 |
The high concentration of description of test: TBF-VII (20000mg/L) aqueous solution, the viscosity of its viscosity and water is close, and easily construction, injection technology are simple.
TBF-VII solution viscosity reduction experimental data table
TBF-VII solution is big more to the viscosity reduction ability of crude oil, and oil displacement efficiency is strong more, and this experiment is in order to screen suitable TBF-VII concentration of aqueous solution, to reach best viscosity reduction and oil displacement efficiency.
Experimental result proves:
-at the mixture of TBF solution with oil, TBF-VII concentration is high, and viscosity break ratio is just high;
-at the mixture of TBF solution with oil, the ratio that crude oil accounts for is high, and viscosity reducing effect is just poor; Under 1: 1 situation of liquid oil ratio, viscosity break ratio＞95%;
-along with the prolongation of time, viscosity break ratio changes little, explains that solution has emulsifying capacity and good stability preferably;
The TBF-VII viscosity reducing effect of-1000mg/L is poor, and the TBF-VII viscosity reducing effect of 1500mg/L and 2000mg/L is similar, considers cost factor, advises the TBF-VII solution of on-the-spot guiding experiment selected 1500mg/L concentration.
TBF-VII type and the contrast of ternary system emulsifying effectiveness
To the emulsifying effectiveness contrast experiment of crude oil, prove that the TBF-VII type has efficient solubilising and emulsified crude oil ability than common ternary oil displacement system (alkylbenzene xanthate, oil xanthate etc.) through TBF-VII type and ternary system.
The Gravity Separation experiment of profit in capillary
Through the experiment of the crude oil Gravity Separation in the capillary, can prove that TBF-VII has stronger permeability, can get into easily in the fine gap of formation rock, and the mother oil displacement in the slit is come out, improve oil displacement efficiency greatly.
When not adding TBF-VII in the capillary, less than 4mm pipe gravitational differentiation difficulty, the 5mm pipe can differentiation through agitating.
When adding the TBF-VII solution of 1500mg/L in the capillary, float to the top greater than the crude oil in the 2mm capillary on all, after 2 hours, the crude oil in the 1mm capillary almost floats to the top on all.
Sudden and violent gas experiment
In order to confirm whether easily breakdown of emulsion of output liquid, and whether the oil behind the breakdown of emulsion, water two meet related request mutually, and the spy carries out aeration experiment.
The TBF-VII aqueous solution of 1500mg/L is mixed with 1: 1,1: 2,1: 3 volume ratio with crude oil, form emulsified solution, this emulsified solution mixes in 1: 2 ratio with formation water, and sudden and violent gas can find out after 4 hours that layering liquid becomes clearly gradually.Crude oil on the glass wall, also wall built-up not gradually.Explain that thinner can form water membrane between crude oil and rock, steel pipe, play good drag reduction washing oil effect.Coalescence is effective, is easy to breaking emulsion and dewatering after the exploitation.
Upper strata after layering oil mensuration is moisture, lower layer of water is measured oil-containing, it is following to record data:
Moisture result sees from oil-containing, the dehydration of this thinner, demulsification reached the oil field with the standard of demulsifier (oil phase is moisture≤30%, water oil-containing≤240mg/L).
Gather and drive under the different recoverys percent of reserves in back TBF-VII and drive and improve the recovery ratio effect comparison for after studying conventional polymer and driving, TBF-VII drives the effect that improves recovery ratio, and gathers and drive the influence that recovery percent of reserves is driven TBF-VII, hereby experiment.
| Polyacrylamide drives the back recovery percent of reserves | TBF-VII drives the back recovery percent of reserves | TBF-VII drives the raising recovery ratio |
| 32.06％ | 65.07％ | 33.01％ |
| 41.79％ | 66.59％ | 24.8％ |
| 52.03％ | 71.86％ | 19.83％ |
The result shows: gather drive the back TBF drive raising recovery ratio＞10%, and gather drive the back recovery percent of reserves high more, the amplitude that TBF further improves recovery ratio is more little.
TBF-VIII's is synthetic
Water with 1/3V (V is the effective volume of agitated reactor) joins in the agitated reactor that said molecular template is housed earlier; Add 3-phenyl-2-propylene-1-sodium sulfonate, 1-thienyl acrylic acid, N-ethyl-(N ', N '-dimethyl-N '-butane group-(4 '-pyrrole radicals) ammonium bromide)-1-sulfydryl acrylamide example (1.0: 1.0: 1.0) in molar ratio again, stir it is dissolved fully; Then with pH value conditioning agent conditioned reaction solution; Making its pH is about 6.0, feeds nitrogen protection, when being heated to 48 ℃; Stirring mixes it, and keeps more than 30 minutes.Then, slowly add the catalyst ammonium persulfate again, reacted about 3.0 hours.
About heat temperature raising to 65 ℃, add pH value conditioning agent, regulating pH is about 11.0, adds initator (ammonium persulfate-sodium sulfite) again, causes copolymerization about 5.0 hours, the reaction end.This product is a TBF-VIII monobasic functional macromolecule aqueous surfactant solution.Through super-dry, obtain pulverous TBF-VIII high molecular polymer product.
The mensuration of TBF-VIII molecular weight:
Press GB 12005.1-89 and G/T12005.10-92 national standard, use determination of ubbelohde viscometer.Use polyacrylamide inherent viscosity method determining molecular weight, in the NaCl of the 30 ℃ of following 1mol/L aqueous solution, measure its [η]=25.32mL/g, be calculated as follows its viscosity average molecular weigh M:
M＝802*[η]
1.25＝802*25.32
1.25＝45551
From the infrared spectrum of TBF-VIII, can find out: 3419cm
-1, 1698cm
-1About be the carboxyl characteristic absorption; 3100-3000cm
-1, 1640cm
-1It is the characteristic absorption of C=C key; 2921cm
-1, 2850cm
-1The peak at place is the characteristic absorption of chain alkyl methylene; 3200cm
-1, 1668cm
-1With 1190cm
-1It is the characteristic absorption of amide groups; 1385cm
-1About be the characteristic absorption of sulfonate; 2483cm
-1Be the sulfydryl characteristic absorption; 1600～1440cm
-1Be the phenyl characteristic absorption; 1602cm
-1, 1488cm
-1, 768cm
-1Be the thienyl characteristic absorption; 1560cm
-1, 1480cm
-1, 1310cm
-1, 1190cm
-1Be the pyrrole radicals characteristic absorption; 1452cm
-1And 3400cm
-1Corresponding to the nitrogen cation; The existence of these characteristic peaks shows groups such as having two keys, amide groups, carboxyl, nitrogen cation, chain alkyl, pyrrole radicals, sulfydryl, thienyl, phenyl, sulfonate in the molecular structure of target product.
The compatibility experimental data of TBF-VIII solution and stratum sewage (being the salt-resistance experiment)
In order to realize directly disposing TBF-VIII solution with oilfield sewage, pollute thereby reduce, the protection environment, thus carry out this compatibility experiment.Use the stratum sewage of 380000mg/L salinity to be mixed with the TBF-VIII solution of concentration as 1500mg/L.Under 25 ℃, at 450nm, after placing different time, measure its absorbance A with spectrophotometer.
| Time (H) | Absorbance (A) | |
| 0 | 1.41 | 0 |
| 24 | 1.40 | -0.01 |
| 48 | 1.45 | 0.04 |
| 72 | 1.42 | 0.01 |
Δ A in the last table representes: the variation difference that absorbance prolongs in time, and its value is more little, and compatibility is good more.
Result of the test shows, the TBF-VIII solution of 1500mg/L concentration, and absorbance prolongs in time big variation does not take place, and proves absolutely that the stratum sewage of TBF-VIII and 350000mg/L salinity is compatibility, has good " salt-resistance ".Can realize fully directly with oilfield sewage configuration TBF-VIII solution.
Sewage and the contrast of distilled water preparation TBF-VIII solution viscosity stability
The viscosity of TBF-VIII solution has a strong impact on the TBF-VIII oil displacement efficiency, so research sewage influences the TBF-VIII solution viscosity.Elder generation's water is mixed with concentration 5000mg/L mother liquor, uses extraction sewage and distilled water respectively with the TBF-VIII solution of mother liquor dilution as 1000mg/L and 1200mg/L then.Oxygen free condition is preserved down, regularly under 45 ℃ of conditions, measures viscosity with Brookfield viscometer, compares.
Result of the test shows, can directly prepare TBF-VIII solution with sewage, and to the not influence of its viscosity.Both practice thrift cost, protected environment again.
Influence detects data to anaerobic bacteria to TBF-VIII
In oilfield sewage, contain a large amount of bacteriums, have very strong bactericidal effect in order to confirm TBF-VIII, the spy carries out this experiment.
Introduced quaternary ammonium salt monomer, thienyl in the TBF-VIII molecular structure, it has the efficient sterilizing effect to sulfate reducing bacteria, has the antibiont degradation characteristic.
TBF-VIII body viscosity data
The viscosity of TBF-VIII solution has decisive influence to the site construction technology flow process of TBF-VIII, so carry out TBF-VIII solution body Study on Viscosity.
| TBF concentration mg/ |
500 | 1000 | 1500 | 2000 | 5000 | 10000 | 15000 | 20000 |
| Viscosity mPa.s | 1.18 | 1.53 | 1.71 | 1.78 | 2.22 | 2.26 | 2.25 | 2.26 |
Description of test TBF-VIII body is under high concentration (20000mg/L), and its viscosity is similar with the viscosity of water, and easily construction, injection technology are simple.
TBF-VIII solution viscosity reduction experimental data table
TBF-VIII solution is big more to the viscosity reduction ability of crude oil, and oil displacement efficiency is strong more, and this experiment is in order to screen suitable TBF-VIII concentration of aqueous solution, to reach best viscosity reduction and oil displacement efficiency.
The experiment proof:
-at the mixture of TBF solution with oil, TBF-VIII concentration is high, and viscosity break ratio is just high;
-at the mixture of TBF solution with oil, the ratio that crude oil accounts for is high, and viscosity reducing effect is just poor; Under 1: 1 situation of liquid oil ratio, viscosity break ratio＞95%;
-along with the prolongation of time, viscosity break ratio changes little, explains that solution has emulsifying capacity and good stability preferably;
The TBF-VIII viscosity reducing effect of-1000mg/L is poor, and the TBF-VIII viscosity reducing effect of 1500mg/L and 2000mg/L is similar, considers cost factor, advises the TBF-VIII solution of on-the-spot guiding experiment selected 1500mg/L concentration.
TBF-VIII type and the contrast of ternary system emulsifying effectiveness
To the emulsifying effectiveness contrast experiment of crude oil, prove that the TBF-VIII type has efficient solubilising and emulsified crude oil ability than common ternary oil displacement system (alkylbenzene xanthate, oil xanthate etc.) through TBF-VIII type and ternary system.
The Gravity Separation experiment of profit in capillary
Through the experiment of the crude oil Gravity Separation in the capillary, can prove that TBF-VIII has stronger permeability, can get into easily in the fine gap of formation rock, and the mother oil displacement in the slit is come out, improve oil displacement efficiency greatly.
When not adding TBF-VIII in the capillary, less than 4mm pipe gravitational differentiation difficulty, the 5mm pipe can differentiation through agitating.
When adding the TBF-VIII solution of 1500mg/L in the capillary, float to the top greater than the crude oil in the 2mm capillary on all, after 2 hours, the crude oil in the 1mm capillary almost floats to the top on all.
Sudden and violent gas experiment
In order to confirm whether easily breakdown of emulsion of output liquid, and whether the oil behind the breakdown of emulsion, water two meet related request mutually, and the spy carries out aeration experiment.
The TBF-VIII solution of 1500mg/L is mixed with 1: 1,1: 2,1: 3 volume ratio with crude oil, form emulsified solution, this emulsified solution mixes in 1: 2 ratio with formation water, and sudden and violent gas can find out after 4 hours that layering liquid becomes clearly gradually.Crude oil on the glass wall, also wall built-up not gradually.Explain that thinner can form water membrane between crude oil and rock, steel pipe, play good drag reduction washing oil effect.Coalescence is effective, is easy to breaking emulsion and dewatering after the exploitation.
Upper strata after layering oil mensuration is moisture, lower layer of water is measured oil-containing, it is following to record data:
Moisture result sees from oil-containing, the dehydration of this thinner, demulsification reached the oil field with the standard of demulsifier (oil phase is moisture≤30%, water oil-containing≤240mg/L).
Gather and drive under the different recoverys percent of reserves in back TBF-VIII and drive and improve the recovery ratio effect comparison
For after studying conventional polymer and driving, TBF-VIII drives the effect that improves recovery ratio, and gathers and drive the influence that recovery percent of reserves is driven TBF-VIII, hereby experiment.
| Polyacrylamide drives the back recovery percent of reserves | TBF-VIII drives the back recovery percent of reserves | TBF-VIII drives the raising recovery ratio |
| 25.39％ | 67.12％ | 41.73％ |
| 38.79％ | 68.03％ | 29.24％ |
| 48.96％ | 70.22％ | 21.26％ |
The result shows: gather drive the back TBF-VIII drive raising recovery ratio＞10%, and gather drive the back recovery percent of reserves high more, the amplitude that TBF-VIII further improves recovery ratio is more little.
The preparation of TBF-IX
Earlier the water with 1/3V (V is the effective volume of agitated reactor) joins in the agitated reactor that said molecular template is housed, example (1.0: 1.0: 1.0) in molar ratio again, add 3-phenyl-2-propylene-1-sodium sulfonate, 1-thienyl acrylic acid, N-ethyl-(N '; N '-dimethyl-N '-pentamethylene base ammonium bromide)-1-(2 '-mercapto-imidazolyl)-acrylamide; Stirring is dissolved it fully, and with pH value conditioning agent conditioned reaction solution, making its pH is about 5.2 then; Feed nitrogen protection; When being heated to 45 ℃, stirring mixes it, and keeps more than 30 minutes.Then, slowly add the catalyst potassium peroxydisulfate again, reacted about 3.0 hours.
About heat temperature raising to 68 ℃, add pH value conditioning agent, regulating pH is about 11.2, adds initator (ammonium persulfate-sodium sulfite) again, causes copolymerization about 5.0 hours, the reaction end.This product is a TBF-IX monobasic functional macromolecule aqueous surfactant solution.After the drying, obtain pulverous pure TBF-IX high molecular polymer.
The mensuration of TBF-IX molecular weight:
Press GB 12005.1-89 and G/T12005.10-92 national standard, use determination of ubbelohde viscometer.Use polyacrylamide inherent viscosity method determining molecular weight, in the NaCl of the 30 ℃ of following 1mol/L aqueous solution, measure its [η]=38.72mL/g, be calculated as follows its viscosity average molecular weigh M:
M＝802*[η]
1.25＝802*38.72
1.25＝77?462。
From the infrared spectrum of TBF-IX, can find out: 3421cm
-1, 1700cm
-1About be the carboxyl characteristic absorption; 3100-3000cm
-1, 1640cm
-1It is the characteristic absorption of C=C key; 2913cm
-1, 2853cm
-1The peak at place is the characteristic absorption of chain alkyl methylene; 3200cm
-1, 1670cm
-1With 1190cm
-1It is the characteristic absorption of amide groups; 1386cm
-1About be the characteristic absorption of sulfonate; 1600～1430cm
-1Be the phenyl characteristic absorption; 1245～1162cm
-1Be the cyclopenta characteristic absorption; 2958cm
-1, 1575cm
-1, 1166cm
-1Be the imidazole ring characteristic absorption; 2484cm
-1Be the sulfydryl characteristic absorption; 1600cm
-1, 1485cm
-1, 770cm
-1Be the thienyl characteristic absorption; 1454cm
-1And 3400cm
-1Corresponding to the nitrogen cation; The existence of these characteristic peaks shows groups such as having two keys, amide groups, nitrogen cation, chain alkyl, sulfonate, sulfydryl, thiophene, imidazole ring, phenyl, cyclopenta in the molecular structure of target product.
The laboratory experiment data:
The compatibility experimental data of TBF-IX solution and stratum sewage (being the salt-resistance experiment)
In order to realize directly disposing TBF-IX solution with oilfield sewage, pollute thereby reduce, the protection environment, thus carry out this compatibility experiment.Use the stratum sewage of 380000mg/L salinity to be mixed with the TBF-IX solution of concentration as 1500mg/L.Under 25 ℃, at 450nm, after placing different time, measure its absorbance A with spectrophotometer.
| Time (H) | Absorbance (A) | |
| 0 | 1.37 | 0 |
| 24 | 1.39 | 0.02 |
| 48 | 1.41 | 0.04 |
| 72 | 1.39 | 0.02 |
Δ A representes in the last table: the variation difference that absorbance prolongs in time, and its value is more little, and compatibility is good more.
Result of the test shows, the TBF-IX solution of 1500mg/L concentration, and its absorbance prolongs in time big variation does not take place, and proves absolutely that the stratum sewage of TBF-IX and 350000mg/L salinity is compatibility, has good " salt-resistance ".Can realize fully directly with oilfield sewage configuration TBF-IX solution.
Sewage and the contrast of distilled water preparation TBF-IX solution viscosity stability
The viscosity of TBF-IX solution has a strong impact on the TBF-IX oil displacement efficiency, so research sewage influences the TBF-IX solution viscosity.Elder generation's water is mixed with concentration 5000mg/L mother liquor, uses extraction sewage and distilled water respectively with the TBF-IX solution of mother liquor dilution as 1000mg/L and 1200mg/L then.Oxygen free condition is preserved down, regularly under 45 ℃ of conditions, measures viscosity with Brookfield viscometer, compares.
Result of the test shows, can directly prepare TBF-IX solution with sewage, and to the not influence of its viscosity.Both practice thrift cost, protected environment again.
Influence detects data to anaerobic bacteria to TBF-IX
In oilfield sewage, contain a large amount of bacteriums, have very strong bactericidal effect in order to confirm TBF-IX, the spy carries out this experiment.
Introduced quaternary ammonium salt monomer, nitrogenous sulfhydryl heterocycle, thienyl in the TBF-IX molecular structure, it has the efficient sterilizing effect to sulfate reducing bacteria, has the antibiont degradation characteristic.
14.2.4TBF-IX body viscosity data
The viscosity of TBF-IX solution has decisive influence to the site construction technology flow process of TBF-IX, so carry out TBF-IX solution body Study on Viscosity.
| TBF concentration mg/ |
500 | 1000 | 1500 | 2000 | 5000 | 10000 | 15000 | 20000 |
| Viscosity mPa.s | 1.53 | 1.62 | 1.71 | 1.83 | 2.15 | 2.46 | 2.57 | 2.56 |
Description of test: the TBF-IX body is under high concentration (20000mg/L), and its viscosity is similar with the viscosity of water, and easily construction, injection technology are simple.
TBF-IX solution viscosity reduction experimental data table
TBF-IX solution is big more to the viscosity reduction ability of crude oil, and oil displacement efficiency is strong more, and this experiment is to select suitable TBF-I X concentration of aqueous solution in order to screen, to reach best viscosity reduction and oil displacement efficiency.
The experiment proof:
-at the mixture of TBF solution with oil, TBF-IX concentration is high, and viscosity break ratio is just high;
-at the mixture of TBF solution with oil, the ratio that crude oil accounts for is high, and viscosity reducing effect is just poor; Under 1: 1 situation of liquid oil ratio, viscosity break ratio＞95%;
-along with the prolongation of time, viscosity break ratio changes little, explains that solution has emulsifying capacity and good stability preferably;
The TBF-IX viscosity reducing effect of-1000mg/L is poor, and the TBF-IX viscosity reducing effect of 1500mg/L and 2000mg/L is similar, considers cost factor, advises the TBF-IX solution of on-the-spot guiding experiment selected 1500mg/L concentration.
TBF-IX type and the contrast of ternary system emulsifying effectiveness
To the emulsifying effectiveness contrast experiment of crude oil, prove that the TBF-IX type has efficient solubilising and emulsified crude oil ability than common ternary oil displacement system (alkylbenzene xanthate, oil xanthate etc.) through TBF-IX type and ternary system.
The Gravity Separation experiment of profit in capillary
Through the experiment of the crude oil Gravity Separation in the capillary, can prove that TBF-IX has stronger permeability, can get into easily in the fine gap of formation rock, and the mother oil displacement in the slit is come out, improve oil displacement efficiency greatly.
When not adding TBF-IX in the capillary, less than 4mm pipe gravitational differentiation difficulty, the 5mm pipe can differentiation through agitating.
When adding the TBF--IX solution of 1500mg/L in the capillary, float to the top greater than the crude oil in the 2mm capillary on all, after 2 hours, the crude oil in the 1mm capillary almost floats to the top on all.
Sudden and violent gas experiment
In order to confirm whether easily breakdown of emulsion of output liquid, and whether the oil behind the breakdown of emulsion, water two meet related request mutually, and the spy carries out aeration experiment.
The TBF-IX aqueous solution of 1500mg/L is mixed with 1: 1,1: 2,1: 3 volume ratio with crude oil, form emulsified solution, this emulsified solution mixes in 1: 2 ratio with formation water, and sudden and violent gas can find out after 4 hours that layering liquid becomes clearly gradually.Crude oil on the glass wall, also wall built-up not gradually.Explain that thinner can form water membrane between crude oil and rock, steel pipe, play good drag reduction washing oil effect.Coalescence is effective, is easy to breaking emulsion and dewatering after the exploitation.
Upper strata after layering oil mensuration is moisture, lower layer of water is measured oil-containing, it is following to record data:
Moisture result sees from oil-containing, the dehydration of this thinner, demulsification reached the oil field with the standard of demulsifier (oil phase is moisture≤30%, water oil-containing≤240mg/L).
Gather and drive under the different recoverys percent of reserves in back TBF-IX and drive and improve the recovery ratio effect comparison
After studying the conventional polymer displacement of reservoir oil, TBF-IX drives the effect that improves recovery ratio, and gathers and drive the influence that recovery percent of reserves is driven TBF-IX, hereby experiment.
| Polyacrylamide drives the back recovery percent of reserves | TBF-IX drives the back recovery percent of reserves | TBF-IX drives the raising recovery ratio |
| 38.59％ | 68.32％ | 29.73％ |
| 43.21％ | 67.63％ | 24.42％ |
| 57.89％ | 69.33％ | 11.44％ |
[0541]The result shows: gather drive the back TBF-IX drive raising recovery ratio＞10%, and gather drive the back recovery percent of reserves high more, the amplitude that TBF-IX further improves recovery ratio is more little.
Embodiment 10
TBF-X's is synthetic
Water with 1/3V (V is the effective volume of agitated reactor) joins in the agitated reactor that said molecular template is housed earlier; Add 2-propylene-1-sodium sulfonate, 1-thienyl acrylic acid, N-ethyl-(N ', N '-dimethyl-N '-pentamethylene base ammonium bromide)-1-(2 '-mercapto-imidazolyl)-acrylamide example (1.0: 1.0: 1.0) in molar ratio again, stir it is dissolved fully; Then with pH value conditioning agent conditioned reaction solution; Making its pH is about 5.7, feeds nitrogen protection, when being heated to 46 ℃; Stirring mixes it, and keeps more than 30 minutes.Then, slowly add the catalyst sodium peroxydisulfate again, reacted about 3.0 hours.
About heat temperature raising to 68 ℃, add pH value conditioning agent, regulating pH is about 11.2, adds initator (ammonium persulfate-sodium sulfite) again, causes copolymerization about 5.0 hours, the reaction end.This product is a TBF-X monobasic functional macromolecule aqueous surfactant solution.Obtain pulverous pure TBF-X high molecular polymer product after the drying.
The mensuration of TBF-X molecular weight:
Press GB 12005.1-89 and G/T12005.10-92 national standard, use determination of ubbelohde viscometer.Use polyacrylamide inherent viscosity method determining molecular weight, in the NaCl of the 30 ℃ of following 1mol/L aqueous solution, measure its [η]=33.66mL/g, be calculated as follows its viscosity average molecular weigh M:
M＝802*[η]
1.25＝802*33.66
1.25＝65?023
From the infrared spectrum of TBF-X, can see: 3422cm
-1, 1702cm
-1Be the carboxyl characteristic absorption; 3100-3000cm
-1, 1643cm
-1It is the characteristic absorption of C=C key; 2912cm
-1, 2851cm
-1The peak at place is the characteristic absorption of chain alkyl methylene; 3200cm
-1, 1669cm
-1With 1191cm
-1About be the characteristic absorption of amide groups; 1386cm
-1About be the characteristic absorption of sulfonate; 2954cm
-1, 1574cm
-1, 1166cm
-1Be the imidazole ring characteristic absorption; 2484cm
-1Be the sulfydryl characteristic absorption; 1600cm
-1, 1486cm
-1, 770cm
-1Be the thienyl characteristic absorption; 1245～1160cm
-1Be the cyclopenta characteristic absorption; 1454cm
-1And 3400cm
-1Corresponding to the nitrogen cation; The existence of these characteristic peaks shows groups such as having two keys, amide groups, nitrogen cation, chain alkyl, sulfonate, imidazole ring, thiophene, sulfydryl, carboxyl, cyclopenta in the molecular structure of target product.
The compatibility experimental data of TBF-X solution and stratum sewage (being the salt-resistance experiment)
In order to realize directly disposing TBF-X solution with oilfield sewage, pollute thereby reduce, the protection environment, thus carry out this compatibility experiment.Use the stratum sewage of 380000mg/L salinity to be mixed with the TBF-X solution of concentration as 1500mg/L.Under 25 ℃, at 450nm, after placing different time, measure its absorbance A with spectrophotometer.
| Time (H) | Absorbance (A) | |
| 0 | 1.40 | 0 |
| 24 | 1.41 | 0.01 |
| 48 | 1.46 | 0.06 |
| 72 | 1.44 | 0.04 |
Δ A in the last table representes the variation difference that absorbance prolongs in time, and its value is more little, and compatibility is good more.
Result of the test shows, the TBF-X solution of 1500mg/L concentration, and big variation does not take place in absorbance, proves absolutely that the stratum sewage of TBF-X and 380000mg/L salinity is compatibility, has good " salt-resistance ".Can realize fully directly with oilfield sewage configuration TBF-X solution.
Sewage and the contrast of distilled water preparation TBF-X solution viscosity stability
The viscosity of TBF-X solution has a strong impact on the TBF-X oil displacement efficiency, so research sewage influences the TBF-X solution viscosity.Elder generation's water is mixed with concentration 5000mg/L mother liquor, uses extraction sewage and distilled water respectively with the TBF-X solution of mother liquor dilution as 1000mg/L and 1200mg/L then.Oxygen free condition is preserved down, regularly under 45 ℃ of conditions, measures viscosity with Brookfield viscometer, compares.
Result of the test shows, can directly prepare TBF-X solution with sewage, and to the not influence of its viscosity.Both practice thrift cost, protected environment again.
Influence detects data to anaerobic bacteria to TBF-X
In oilfield sewage, contain a large amount of bacteriums, have very strong bactericidal effect in order to confirm TBF-X, the spy carries out this experiment.
Introduced quaternary ammonium salt monomer, nitrogenous sulfhydryl heterocycle, thienyl in the TBF-X molecular structure, it has the efficient sterilizing effect to sulfate reducing bacteria, has the antibiont degradation characteristic.
TBF-X body viscosity data
The viscosity of TBF-X solution has decisive influence to the site construction technology flow process of TBF-X, so carry out TBF-X solution body Study on Viscosity.
| TBF concentration mg/ |
500 | 1000 | 1500 | 2000 | 5000 | 10000 | 15000 | 20000 |
| Viscosity mPa.s | 1.42 | 1.60 | 1.76 | 1.82 | 2.19 | 2.61 | 2.52 | 2.54 |
Description of test: the TBF-X body is under high concentration (20000mg/L), and its viscosity is similar with the viscosity of water, and easily construction, injection technology are simple.
TBF-X solution viscosity reduction experimental data table
TBF-X solution is big more to the viscosity reduction ability of crude oil, and oil displacement efficiency is strong more, and this experiment is to select suitable TBF-X concentration of aqueous solution in order to screen, to reach best viscosity reduction and oil displacement efficiency.
The experiment proof:
-at the mixture of TBF solution with oil, TBF-X concentration is high, and viscosity break ratio is just high;
-at the mixture of TBF solution with oil, the ratio that crude oil accounts for is high, and viscosity reducing effect is just poor; Under 1: 1 situation of liquid oil ratio, viscosity break ratio＞95%;
-along with the prolongation of time, viscosity break ratio changes little, explains that solution has emulsifying capacity and good stability preferably;
The TBF-X viscosity reducing effect of-1000mg/L is poor, and the TBF-X viscosity reducing effect of 1500mg/L and 2000mg/L is similar, considers cost factor, advises the TBF-X solution of on-the-spot guiding experiment selected 1500mg/L concentration;
TBF-X type and the contrast of ternary system emulsifying effectiveness
To the emulsifying effectiveness contrast experiment of crude oil, prove that the TBF-X type has efficient solubilising and emulsified crude oil ability than common ternary oil displacement system (alkylbenzene xanthate, oil xanthate etc.) through TBF-X type and ternary system.
The Gravity Separation experiment of profit in capillary
Through the experiment of the crude oil Gravity Separation in the capillary, can prove that TBF-X has stronger permeability, can get into easily in the fine gap of formation rock, and the mother oil displacement in the slit is come out, improve oil displacement efficiency greatly.
When not adding TBF-X in the capillary, less than 4mm pipe gravitational differentiation difficulty, the 5mm pipe can differentiation through agitating.
When adding the TBF-X solution of 1500mg/L in the capillary, float to the top greater than the crude oil in the 2mm capillary on all, after 2 hours, the crude oil in the 1mm capillary almost floats to the top on all.
Sudden and violent gas experiment
In order to confirm whether easily breakdown of emulsion of output liquid, and whether the oil behind the breakdown of emulsion, water two meet related request mutually, and the spy carries out aeration experiment.
The TBF-X aqueous solution of 1500mg/L is mixed with 1: 1,1: 2,1: 3 volume ratio with crude oil, form emulsified solution, this emulsified solution mixes in 1: 2 ratio with formation water, and sudden and violent gas can find out after 4 hours that layering liquid becomes clearly gradually.Crude oil on the glass wall, also wall built-up not gradually.Explain that thinner can form water membrane between crude oil and rock, steel pipe, play good drag reduction washing oil effect.Coalescence is effective, is easy to breaking emulsion and dewatering after the exploitation.
Upper strata after layering oil mensuration is moisture, lower layer of water is measured oil-containing, it is following to record data:
Moisture result sees from oil-containing, the dehydration of this thinner, demulsification reached the oil field with the standard of demulsifier (oil phase is moisture≤30%, water oil-containing≤240mg/L).
Gather and drive under the different recoverys percent of reserves in back TBF-X and drive and improve the recovery ratio effect comparison
For after studying conventional polymer and driving, TBF-X drives the effect that improves recovery ratio, and gathers and drive the influence that recovery percent of reserves is driven TBF-X, hereby experiment.
| Polyacrylamide drives the back recovery percent of reserves | TBF-X drives the back recovery percent of reserves | TBF-X drives the raising recovery ratio |
| 36.23％ | 63.72％ | 27.49％ |
| 45.62％ | 66.39％ | 20.77％ |
| 56.39％ | 68.06％ | 11.67％ |
[0591]The result shows: gather drive the back TBF-X drive raising recovery ratio＞10%, and gather drive the back recovery percent of reserves high more, the amplitude that TBF-X further improves recovery ratio is more little.
Claims (8)
1. functional macromolecule surfactant, it has general formula (1):
Formula (1)
R wherein
1Be selected from H, phenyl, benzene sulfonate; R
2Be selected from H, sulfydryl, nitrogenous sulfhydryl heterocycle; R
3Be selected from H, phenyl, nitrogenous sulfhydryl heterocycle, imidazoles, thiophene; R
4Be selected from quaternary ammonium salt;
The molecular weight of this functional macromolecule surfactant is 20,000 to 1,000 ten thousand.
2. functional macromolecule surfactant as claimed in claim 1, wherein said quaternary ammonium salt has functional group.
3. functional macromolecule surfactant as claimed in claim 2; The functional group of wherein said quaternary ammonium salt is selected from one or more in following: carboxylic acid group, sulfonic group, cycloalkyl, alkyl, pyridine, pyrroles, alkyl-carboxylic acid, sulfonic alkyl, cycloalkyl-alkyl, pyridine alkyl and pyrrolidinyl; Wherein said cycloalkyl is the cycloalkyl of 5 yuan or 6 yuan, and said alkyl is the alkyl of 3-18 carbon atom.
4. functional macromolecule surfactant as claimed in claim 3, wherein said alkyl are the alkyl of 3-16 carbon atom.
5. functional macromolecule surfactant as claimed in claim 3, wherein said alkyl are the alkyl of 8-16 carbon atom.
6. like each described functional macromolecule surfactant among the claim 1-3, wherein said nitrogenous sulfhydryl heterocycle is a mercaptoimidazole.
7. the purposes of the described functional macromolecule surfactant of claim 1, it is used for, and three oil exploitations, oily waste water treatment, oily sludge are handled, the oil-containing Seawater Treatment, or as drilling mud additives.
8. purposes as claimed in claim 7, it is used for three oil exploitations, oily waste water treatment, oily sludge processing or oil-containing Seawater Treatment.
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