• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:

    公开号:SU1207398A3
    申请号:SU823460066
    申请日:1982-06-30
    公开日:1986-01-23
    发明作者:Энгельхардт Фридрих；Ригель Ульрих；Хилле Мартин；Витткус Хейнц
    申请人:Касселла Аг.(Фирма)；
    IPC主号:
    专利说明:

    The invention relates to the drilling of oil and gas wells, in particular to drilling flushing fluids, and can be used for flushing with water suspensions of deep wells with high temperatures and highly mineralized formation waters.
    The purpose of the invention is to increase the stability of the suspension to high temperatures and electrolyte concentrations.
    In the proposed method of flushing drilling boreholes as a flushing; 1 shd; awns are used water-suspension of the usual swellable minerals, solids, such as glia, mainly bentonites, and in the corresponding case, increase the density of water-insoluble additives For example, kalid carbonate, barium sulphate or iron oxides, stabilized with an organic additive — a water-soluble copolymer — an amount of 0.5–40 kg / m, consisting of 10–95 wt.% of the fortiutyl residues by the static distribution.
    si
    sn
     one

    HN-ClCH-CH 5-50 wt.% From the remainder of the formula
    -N-k
    one
    D
    co-in
    and 0-80 wt.% of the residues of the structural formula
    -SNO-Sht o. nng
    where R and R are the same or different and denote hydrogen, methyl or ethyl; X is a sodium or potassium cation, if SH-1MONIUM, or dimethyloxyethyl ammonium.
    Production of water-soluble & gx copolymers according to the proposed method is possible, if for the purpose of preparation
    100 wt-h to dissolve copolymer in water or water-miscible organic solvent from 10 to 95 wt.h. 2-acrylamido-2-methyl- -propanesulfonic acid- (3) structural formula (I)
    CV.Cti CO-W-c (,, H ,,
    then neutralize by adding sulfonic acid base, then add from 5 to 50 wt.h. vinylacylamide structural formula II,,
    one
    20
    R
    CH2 CH-N-CO H
    five
     where R. and K are the same shsh different: and denote hydrogen,
    methyl or ethyl,
    add in the appropriate case from 0 to 80 ma.ch. acrylamide, after which you can begin to conduct copolymerisation in a known manner at 10-120 C.
    The copolymers according to the proposed method are obtained by using 100 wt.h for the formation of a copolymer. from 30 to 70 ma.ch. 2-acrylamido-2-methyl-β-propanesulfonic acid- (3) structural formula 1, from 01 to 30 parts by weight. Vinyl acrylamide of structural formula II and, as appropriate, from 0 to 60 wt.h. Accord shda Water-miscible organic solvents, in particular, include water-soluble alkanols with the number of C 1-4 atoms: methanol, ethanol, propanol, -propanol, H-, sec - and 0 0-butanol,. preferably, however, a t-butt NOL.
    The water content of low alkanols used as solvents should not exceed wt.%, Since otherwise lumping may occur during pripolymerization. Preferably work with a water content of 0-3%,
    The amount of solvent used depends to some extent on the type of comonomer used.
    As a rule, 200-1000 g of solvent are used per 100 g of the total amount of monomers.
    13
    0
    five
    It is advisable to choose the base to neutralize 2-acrylamido-2-methyl-propanesulfonic acid (3) so that it gives the desired cation X. Therefore, a weak acid salt, an alkali metal hydroxide, or the compound of the formula NR, and the three residues R are the same and different and denote hydrogen, alkyl with the number of C 1-4 or oxethyl atoms.
    As a rule, it is preferable to use the sodium or potassium salt of a weak acid, sodium or potassium hydroxide as a base, if the products are intended to be used as auxiliary substances in drilling without the use of solid materials.
    As usual, the polymerization is carried out in a protective gas atmosphere, preferably nitrogen. Polymerization temperature ranges from 20-120 seconds, preferably AO-BOO C.
    In order to initiate polymerization, high energy electromagnetic rays can be used or conventional polymerization initiators, for example organic peroxides, such as benzoyl peroxide, tert-butyl hydroperoxide, methyl ethyl ketone peroxide, cumene hydroperoxide, azo compounds, azo-di-iso-butyroxy nitrile as well as inorganic peroxide compounds, such as (NH) 2S20g, or, or HjOj, in appropriate cases, in combination with reducing agents, like sodium hydrosulfite or the same redox systems that contain Restores the component aliphatic and aromatic sulfinic acids as benzolsul Finns and toluenesulfinic acid or derivatives of these acids such as, for example, Mannich adtsukty of Finns sulfonic acids, aldehydes and amnno- compounds. Per 100 g of the total mass of monomers, as a matter of fact, 0.05-2 g of a polymerization initiator is used.
    In the case of using water as a solvent, the polymerization takes place under solution polymerization conditions to produce a watery viscous solution of the copolymerisate, from
    which product is isolated by distilling off water or by precipitating by mixing the solution with a water-miscible organic solvent, such
    like methanol, ethanol, acetone or the like. It is preferable, however, that the resulting aqueous solution is used directly according to its intended purpose when the required concentration is reached.
    When copolymerized in the above organic solvents, preferably Tiper -butanol, the polymerization is carried out by precipitation. Wherein
    the polymerizate precipitates as a solid, so that it can be isolated by distilling off the solvent or by suction and drying. The proposed copolymers in drilling flushing fluids have a very good effect as protective colloids both at high temperatures and at high concentrations of electrolytes and litas, superior in stability
    to the electrolytes and stareshpo the substantially closest known substances used as additives to drilling flushing fluids.
    Example 1. Before using the drilling fluid, it is necessary to check its properties for stability by at least one of the indicated experiments on models. At the same time, the suitability of drilling drilling fluid and, mainly, of the added copolymerisate, in terms of filtrate, is determined according to the American Standard American Petroleum Jndustrie Code 29.
    Samples of drilling drilling fluids containing 4% bentonite and water that is virtually free of electrolytes, as well as drilling mud with 25% sodium chloride and 1% gypsum are added in each case, 7, additives A – D. The flushing fluid, which is virtually free of electrolytes, has a filtration rate of 24 cm, and the flushing
    liquids with 25% sodium chloride and 1% gypsum - 63 cm. Indicators of fshhtratration according to the standard AP1 in normal conditions (20 C) 1G after thermostating at 15 h
    at 200 ° C are measured and recorded.
    The test results are summarized in table 1.
    five
    Example 2 In a sample of borax, a washing liquid containing 4% bentonite, 10% sodium chloride and 10% calcium chloride, in the case of 2% additives A – D. The filtration rate of flush liquor without additives is 72 cm. The tests are carried out as in Example 1.
    The test results are summarized in table 2.
    The test results show the superiority of the proposed compounds A and B over the well-known, still resistant to high temperatures additives to the washing fluids C, D and E. Table 1 shows their approximate equivalence in water based drilling fluids based on actually electrolytes. In drilling muds of salt water, the efficiency of Au and B products is clearly expressed. Particularly high superiority is given to mixed polymers A and B when washing, the kidneys, as in Example 2, contain, along with sodium chloride, also calcium chloride. Compounds C and E at the same time fail due to their sensitivity to calcium ions, while copolymer D does not achieve the effectiveness of mixed polymers A and B.
    For comparison tests, the following additives are used.
    A. Mixed polymerizate (prepositional), consisting of 65% Al-HIK (2-acrylamido-2-metsh-propanesulfonic acid), 20% N-vinyl-N-methyl acetamide, 15% acrylamide.
    B, a mixed polymer (proposed) consisting of 80% AMPK, 20% K-vinnl S methylacetamide.
     C. mixed polymerizat, consisting of ac-1y of sodium acrylate, acrish-1ida 3, example 2, product No. 5 (comparative),
    D. Mixed polymerizate, consisting of pz 45% sodium vinyl sulfonate, 55% K-vinyl H-methylacetamide lj
    E. Mixed polymerizate consisting of 20% sodium vinyl sulphonate, 70% acrylamide, 10% N-vinylpyrrolidone 2.
    Used in these experiments according to the proposed method, the additive is obtained as follows
    073986
    In a 2 l polymerization flask equipped with a stirrer, a reflux condenser, a dropping funnel, an inlet for gas and water, an electrically heated 5% bath is charged with 600 ml of tert-butanol, a solution in it of 65 mg M-HQ with stirring, after of which a solution of 17 g of hydroxide is added dropwise.
    10 potassium in 60 ml of water, followed by the addition of 15 g of acrylamide and 20 g of N-vinyl-K-methylacetamide. When nitrogen is introduced, the reaction mixture is heated using an electric
    15 baths up to 50 ° С, then adding 1.0 g of azo-iso-butyronitrile. After an induction period of about 2 hours, the polymerization begins, the reaction temperature. rises to 69 ° C, polymerizate
    20 falls out. It is then heated for 2 hours at 80 ° C to obtain a thick slurry. Polpcher is isolated by suction and drying in vacuum at 50 ° C. The solvent, however, can be distilled off.
    25
    directly under reduced pressure from the reaction mixture. The polymer is obtained in the form of a white light powder, well soluble in water. The K value according to Fickencher is 170.
    0
    five
    0
    If 80 g of AMPK and 20 g of N-vinyl-N-methylacetamide are polymerized in a similar way, then npj-i-variable proposed additive B is obtained.
    Example 3. a) Wash fluid with a content of 4% bentonite and water containing almost no electrolytes, as well as a drilling fluid with a content of 25% sodium chloride and 1% ninca, is added 1% each according to the proposed spray method E The drilling mud, which is practically free of electrolytes, without an additive additive w-ieeT, the filtration rate is 24 cm, and the drilling fluid containing 25% sodium chloride and 1% gypsum is 63 cm. The filtration indexes according to API were measured under normal conditions () and after thermostating for 15 hours at 200 ° C.
    The filtration rate according to API under usual conditions for a is 8.2, for S 6.8, after thermostatting / 9.0, for S 8.0, where a is washing water with water; containing electrolytes, b - flushing fluids with
    25% sodium chloride 1% gypsum.
    b) Applied in example 3 for CL Supplement E is obtained as follows,
    A polymerization flask with a capacity of 2 liters and equipped with a stirrer, a reflux condenser, a dropping funnel, a gas supply tube and an electrically heated water bath is charged with 600 ml of tert-butane, in which 79 g of AMPA are weighed, with stirring, l of ammonia gas and add 1.0 g of acrylamide and 20 g of N-BINYL-N-methylacetamide. Entering the nitrogen, the reaction mixture is heated by means of an electrically heated bath to 50 ° C, then 1.0 azo-iso-butyronitrile 1 is added. After a period of induction of about 2 hours, polymerization begins, the reaction temperature rises to 69 ° C, and the polymerizate precipitates. Then they are still mixed for 2 hours at 80 ° C with the formation of a thick suspension liquid. The polymer was sucked off and dried at 50 ° C under vacuum. However, there is also the possibility of direct distillation of the solvent under reduced pressure from the reaction mixture. The polymer is obtained in the form of a Belgo light powder, well soluble in water, the K value according to Fikentcher 190.
    Example 4. In a drilling fluid with a content of 4% bentonite, 10% sodium chloride and 10% calcium chloride, 2% of copolymer E is added. The filtration rate of the drilling fluid without additives is 72 cm. The tests are carried out as in Example 1.
    API filtering rate, cm, under normal conditions, is 5.0, aging is 5.5.
    Example 5. Of the three tests in the open field, samples I, II and III of the used drilling fluids were taken with a trace} of the total composition.
    I. Morska water: approximately 4% by weight of bentonite, approximately 30% by weight of heavy spar (barium sulfate) and approximately 4% by weight of solids obtained during drilling.
    L
    II. Water saturated with sodium chloride: about 3% by weight of bentonite, about 4% by weight
    2073988
    drilling solids.
    Iii. Water on a 20% by weight calcium chloride: approximately 5 to 50% by weight chalk, approximately 0.2 to 0.5% by weight, obtained by drilling solids.
    For all three samples, the filtration index was determined according to API and gph 10 conditions with high temperature and high pressure of approximately 150 ° C and 35 bar. Then, additive A is added as proposed. the method for sample I 8 kg / m, for sample 15 II 26 kg / m and for sample III 36 kg / m.
    Table 3 shows the physical properties of drilling solutions.
    For all three drilling fluids, thereafter set again 20 the filtration rate by API and under conditions of high temperature and high pressure and 35 bar. The results are shown in table 4.
    25 If only 4 kg / m of the proposed additive A is added to the drilling fluid I, then a filtration index of 0 cm is set at API, 2 cm and under conditions at high temperature and high pressure (150 C / 35 bar) 34 cm. Similarly, to obtain the additives listed in Table 5 and apply them according to the invention. In tab. 5 and 6 are abbreviations: AM - acrylam-1;
    BMA - N-vinyl-N-methyl-acetamide; AMPK - 2-acrylam-2-2-methyl- -propanesulfonic acid- (3), and the indicators indicate: 1 - ammonium salt, 2 - dimethyl- / 5-hydroxyethyl ammonium salt, 3 - potassium salt, 4 - sodium salt, VA - Vinylacetamide; HF - vinylformamide, A - ammonium peroxide disulfate;
    B - ammonium peroxydisulolate + dibutylamine ammonium chloride +
    thirty
    -S02-CH-NH-COOCH3 COOH
    with - azoisobutyronitrile.
    PRI m e. R 32. The proposed copolymerizate can be obtained also in the aquatic environment. At the same time, they work similarly to the following prescription for manufacturing.
    in Example 1, a device of 28 ml (25%) ammonia solution is added to 200 ml of deiopizironannogo water, after which 65 g AMPK are added with stirring and introducing a weak stream of nitrogen. Upon formation of a clear solution, 15 g of acylamide and 20 g of N-vinll-N-methane acetamide are added, pH of the solution is 8.0. By adding 10 ml of a 0.5% aqueous solution of mmonium peroxydisulphate, the polymerization process is initiated. At the end of the induction period, about 40 minutes poly120739810
    the merization begins, the temperature rises to 42 ° C, the reaction mixture becomes viscous. Then it is further heated for 2 hours at 80 ° C. 5 A clear, highly viscous solution is obtained with a K nQ value of Fickencher 250, which can immediately be used as an additive to drilling fluid.
    In a similar way, it is possible to synthesize copolymerizates (Table 6), which are very suitable for the proposed method.
    Table 1
    Wash fluids that do not actually contain
    electrolytes.
    Flushing liquids, capacities containing 25% sodium chloride and 1% gypsum,
    Table 2
    No additive
    With additive as suggested75
    87
    Table 3
    Table 4
    95
    100
    100
    100
    13
    120739a
    27
    177
    , 10 90
    14 Continuation of table 5
    43
    142.5
    35 65
    44
    120
    50 50
    Hjo
     II
     II
    权利要求:
    Claims (1)
    [1]
    “WAY OF DRILLING DRILLING 'WELLS, which use an aqueous suspension of swellable mineral solids and, if appropriate, increase the density of water-insoluble additives and organic additives, characterized in that, in order to increase the stability of the suspension to high temperatures and electrolyte concentrations, as an organic additives use a water-soluble copolymer consisting of a residual of the general formula according to a statistical distribution of 1095 wt.%.
    “CHO-CH1 co
    HN-C (CH 3 ) 2-CH 2 - SO3X® for 5-50 wt.% From the residues of the General formula
    -sn 2 -sn1-1
    CO-R 2 and 0-80 wt.% From the residues of the formula
    -sn 2 -sn- “
    0 = 0 where R 1 and R 2 are the same or different and mean hydrogen, methyl or ethyl;
    X® is a cation of sodium or potassium, or ammonium, or dimethyloxyethylammonium.
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    申请号 | 申请日 | 专利标题
    DE19792931897|DE2931897A1|1979-08-06|1979-08-06|WATER-SOLUBLE COPOLYMER AND ITS PRODUCTION|
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