A kind of drilling fluid tackifier that helps protecting hydrocarbon zone
Technical field:
The present invention relates to a kind of drilling fluid tackifier that helps protecting hydrocarbon zone, belong to oil field drilling fluids additive technology field.
Background technology:
Conventional at present water-base drilling fluid adopts water-soluble polymer usually, and is formulated as tackifier as hydro-polyacrylamide, carboxymethyl cellulose, modification guanidine glue etc.There is the problem that can not thoroughly break glue in these water-base drilling fluids in the completion later stage, and in a single day polymer is squeezed into the stratum and very easily is adsorbed, is trapped in the hole, causes oily stream to be obstructed, and cause oil well productivity to descend.At this problem, at present conventional solution is to adopt chemical gel breaker thoroughly to break glue, is in a single day adsorbed, is trapped in the hole by the stratum to prevent the water-soluble polymer in the water base drilling fluid, causes the be obstructed generation of situation of oily stream.But its drawback of this solution is chemical gel breaker is generally oxygenant, all has unsafe factor in transportation and the use, can't satisfy the requirement of engineering of drilling safety operation.
Summary of the invention:
The objective of the invention is to: provide a kind of by tetrapolymer with diquaternary amine salt is composite forms; in the aqueous solution, form micellar solution; when micellar concentration surpasses threshold value; intermolecular formation space grid structure; thereby soltion viscosity is increased considerably, and have stronger suspending power, run into oil gas and can break glue automatically; protect hydrocarbon zone to greatest extent, improve oil well productivity.Thoroughly solve the drilling fluid tackifier that helps protecting hydrocarbon zone that existing drilling liquid water soluble macromolecular tackifier can not thoroughly break the glue problem.
The present invention realizes above-mentioned purpose by following technical solution:
A kind of drilling fluid tackifier that helps protecting hydrocarbon zone, it is characterized in that: it is made of following components in part by weight:
5~95 parts of tetrapolymers
95~5 parts of diquaternary amine salt;
Described tetrapolymer is polymerized by three kinds of vinyl monomers and a kind of hydrophobic monomer, and the quality proportioning of three kinds of vinyl monomers and a kind of hydrophobic monomer is: 20~30: 30~20: 47~45: 3~5;
Described three kinds of vinyl monomers are any three kinds in acrylamide, vinylformic acid, 2-acrylamido-2-methyl propane sulfonic acid, sodium p styrene sulfonate, N,N-DMAA, sodium allylsulfonate, methylene-succinic acid, the fumaric acid;
Described hydrophobic monomer is any one in 2-acrylamido dodecane sulfonic acid, N-dodecyl acrylamide, N-hexadecyl acrylamide, the single toxilic acid hexadecyl of N-acid amides, the single toxilic acid octadecyl of the N-acid amides;
Described diquaternary amine salt is: N, N '-two (tetradecyl dimethyl)-1,3-dibrominated propane-diammonium salt, N, N '-two (hexadecyldimethyl benzyl ammonium)-1,2-dibrominated second di-ammonium salts, N, N '-two (dodecyl dimethyl)-1,2-dibrominated second di-ammonium salts, N, N '-two (dodecyl dimethyl)-1,3-dibrominated propane-diammonium salt, N, N '-two (hexadecyldimethyl benzyl ammonium)-1, any one in the 3-dibrominated propane-diammonium salt.
Above-mentioned help protecting the preparation method of the drilling fluid tackifier of hydrocarbon zone to be:
(1), produce tetrapolymer:
Getting 300 ml deionized water pours in the clean wide-necked bottle, add 5 gram sodium hydroxide, stirring is dissolved sodium hydroxide fully, be 20~30: 30~20 according to mass ratio successively then: 47~45: 3~5 proportioning is got acrylamide, vinylformic acid, 2-acrylamido-2-methyl propane sulfonic acid, sodium p styrene sulfonate, N, the N-DMAA, sodium allylsulfonate, methylene-succinic acid, any three kinds of raw materials and 2-acrylamido dodecane sulfonic acid in the fumaric acid, N-dodecyl acrylamide, N-hexadecyl acrylamide, the single toxilic acid hexadecyl of N-acid amides, any one raw material in the single toxilic acid octadecyl of the N-acid amides, making four kinds of total quality of monomer is 100 grams, join in the wide-necked bottle, stir, four kinds of monomers are dissolved fully till.Regulate the pH value of mixed solution 4~6 with 10% sodium hydroxide solution again, logical at ambient temperature nitrogen is after 30 minutes, Potassium Persulphate and 0.2~0.4 gram S-WAT with 0.4~0.8 gram carry out polyreaction as initiator, after the question response time reaches 6 hours, polyreaction is finished, generate low-molecular weight polymer, spray-dried then, pulverize, cross 40 mesh sieves and promptly get tetrapolymer, standby;
(2), produce drilling fluid tackifier:
Tetrapolymer is mixed by said ratio and diquaternary amine salt, pulverize the back and cross 40 mesh sieves, be drilling fluid tackifier product of the present invention.
The present invention's beneficial effect compared with prior art is:
1, this product is low-molecular weight polymer by the polymkeric substance of extraordinary vinyl monomer with diquaternary amine salt is composite forms, and forms micellar solution by molecular association in the aqueous solution, plays tackify and proposes the effect of cutting, and its micella mainly is earthworm shape or oval bar-shaped; Because the hydrophobic association effect, when micellar concentration surpasses threshold value, intermolecular formation space grid structure, thus soltion viscosity is increased considerably and have certain elasticity and stronger suspending power, satisfying the requirement of engineering of drilling operation,
2, running into oil gas when going into operation can break glue automatically, does not need chemical gel breaker, just can remove the pollution of drilling fluid to oil reservoir.The clay and the high-molecular weight polymer that adopt this drilling fluid tackifier to substitute in the conventional drilling liquid make up drilling fluid system, help protecting hydrocarbon zone.
3, drilling fluid tackifier of the present invention is compared with conventional drilling liquid tackifier, except that containing hydrophilic radical, also contains the hydrophobic grouping of long carbochain, can reduce the surface tension of drilling fluid, effectively prevents the water lock, improves oil well productivity.
Embodiment:
Below in conjunction with specific embodiment the present invention is further described.
Embodiment 1:
Vinyl monomer is got vinylformic acid, sodium p styrene sulfonate, 2-acrylamido-2-methyl propane sulfonic acid; Hydrophobic monomer is got the single toxilic acid hexadecyl of N-acid amides; Diquaternary amine salt is got N, N '-two (hexadecyldimethyl benzyl ammonium)-1,3-dibrominated propane-diammonium salt.
(1), produce tetrapolymer:
In the reaction vessel of cleaning, add an amount of 300 milliliters deionized water successively, 5 gram sodium hydroxide stir, get vinylformic acid 28 grams successively, sodium p styrene sulfonate 22 grams, 2-acrylamido-2-methyl propane sulfonic acid 47 grams, the single toxilic acid hexadecyl of N-acid amides 3 grams, join in the wide-necked bottle, stir, till monomer is dissolved fully, regulate the pH value of above-mentioned mixed solution 4 with 10% sodium hydroxide solution again, logical at ambient temperature nitrogen is after 30 minutes, carry out polyreaction with 0.4 gram Potassium Persulphate and 0.2 gram S-WAT as initiator, behind the confined reaction 6 hours, generate low-molecular weight polymer, spray-dried then, pulverize, cross 40 mesh sieves and promptly get tetrapolymer, standby;
(2), produce drilling fluid tackifier:
Get 50 parts of weight parts of synthetic tetrapolymer and N, N '-two (hexadecyldimethyl benzyl ammonium)-1,50 parts of weight parts of 3-dibrominated propane-diammonium salt mix, and pulverize the back and cross 40 mesh sieves, promptly make drilling fluid tackifier product of the present invention.
Embodiment 2:
Vinyl monomer is got acrylamide, N,N-DMAA, sodium allylsulfonate; Hydrophobic monomer is got N-dodecyl acrylamide; Diquaternary amine salt is got N, N '-two (dodecyl dimethyl)-1,2-dibrominated second di-ammonium salts.
(1), produce tetrapolymer:
In the reaction vessel of cleaning, add an amount of 300 deionized water successively, 5 gram sodium hydroxide stir, get acrylamide 23 grams successively, N, N-DMAA 27 grams, sodium allylsulfonate 46 grams, N-dodecyl acrylamide 4 grams join in the wide-necked bottle, stir, till monomer is dissolved fully, sodium hydroxide solution with 10% is regulated the pH value of mixed solution 5, logical at ambient temperature nitrogen is after 30 minutes, carry out polyreaction with 0.6 gram Potassium Persulphate and 0.3 gram S-WAT as initiator, behind the confined reaction 6 hours, generate low-molecular weight polymer, spray-dried then, pulverize, cross 40 mesh sieves and promptly get tetrapolymer, standby;
(2), produce drilling fluid tackifier:
Get 80 parts of weight parts of synthetic tetrapolymer and N, N '-two (dodecyl dimethyl)-1,20 parts of weight parts of 2-dibrominated second di-ammonium salts mix, and pulverize the back and cross 40 mesh sieves, promptly make drilling fluid tackifier product of the present invention.
This helps protecting the beneficial effect of the drilling fluid tackifier of hydrocarbon zone for further proof, and the performance of this drilling fluid tackifier has been carried out indoor evaluation, and its concrete outcome is as follows:
1, the performance evaluation of drilling fluid tackifier:
The indoor tackify situation of different dosage tackifier in seawater of having estimated, experimental result such as table 1:
The tackify characteristic of the different dosage tackifier of table 1 in seawater
Dosage |
??AV??(mPa·s) |
??PV??(mPa·s) |
??YP(Pa) |
??Ф6/Ф3 |
??0.2% |
??10 |
??6 |
??4 |
??2/1 |
??0.5% |
??18 |
??12 |
??6 |
??4/3 |
??0.8% |
??30 |
??16 |
??14 |
??10/9 |
??1.0% |
??35 |
??19 |
??16 |
??12/11 |
Experimental data shows that tackifier of the present invention all have tackify effect preferably in seawater, owing to the intermicellar mutual association of molecule forms network structure, thereby has higher yield value, helps the rock of taking of Multilateral Wells.
2, the water-base drilling fluid fundamental property is estimated:
With tackifier of the present invention is the core processing agent, and the water-base drilling fluid system formulation of structure is as follows:
Seawater+0.15%NaCO
3+ 0.3%NaOH+1.0%~1.5% tackifier+2% fluid loss agent FL+3% polymeric alcohol JLX+3%KCl+5% plugging agent QWY (200 order).
Table 2 water-based drilling liquid system fundamental property
Experiment condition |
??AV??mPa.s |
??PV??mPa.s |
??YP??Pa |
??YP/??PV |
??Ф6/??Ф3 |
??FL
API??ml
|
??FL
HTHP??ml
|
Before rolling |
??33 |
??14 |
??19 |
??1.36 |
??12/10 |
|
|
After rolling |
??36 |
??17 |
??19 |
??1.12 |
??14/12 |
??4.8 |
??10 |
Aging condition: 100 ℃ * 16h.
As can be seen, the water-base drilling fluid of structure has good rheological and good dehydration building capacity, can satisfy the oil gas drilling requirement from above experimental result.
5, water-base drilling fluid reservoir protection performance evaluation
Assessment process is carried out according to China National Petroleum industry standard SY/T6540-2002 " damage of drilling fluid and completion fluid oil reservoir indoor evaluation method ", and the dynamic filter press of employing High Temperature High Pressure is simulated under the drilling condition and the High Temperature High Pressure rock core flows, and instrument is estimated the reservoir protection performance of drilling fluid.Table 3 experimental result shows: two core permeability recovery values show that all more than 90% the water-based drilling liquid system that is made up by tackifier of the present invention has reservoir protection performance preferably.
Table 3 water-based drilling liquid system rock core flowing experiment result
Rock core number |
??2984 |
??2875 |
?Ko,10
-3μm
2 |
??85.8 |
??96.4 |
?K
1,10
-3μm
2 |
??78.5 |
??91.1 |
Permeability resume figure Krd, % |
??91.5 |
??94.5 |
Annotate: it is 100 ℃ of temperature, pressure 3.5MPa, time 125min that drilling fluid dynamically pollutes experiment condition.