CN115895610B - Waterproof locking agent for drilling well and preparation method and application thereof - Google Patents

Waterproof locking agent for drilling well and preparation method and application thereof Download PDF

Info

Publication number
CN115895610B
CN115895610B CN202111165552.4A CN202111165552A CN115895610B CN 115895610 B CN115895610 B CN 115895610B CN 202111165552 A CN202111165552 A CN 202111165552A CN 115895610 B CN115895610 B CN 115895610B
Authority
CN
China
Prior art keywords
drilling
lignin
waterproof
lignosulfonate
agent according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202111165552.4A
Other languages
Chinese (zh)
Other versions
CN115895610A (en
Inventor
褚奇
石秉忠
李涛
李胜
徐江
刘金华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Research Institute of Petroleum Engineering
Original Assignee
China Petroleum and Chemical Corp
Sinopec Research Institute of Petroleum Engineering
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Research Institute of Petroleum Engineering filed Critical China Petroleum and Chemical Corp
Priority to CN202111165552.4A priority Critical patent/CN115895610B/en
Publication of CN115895610A publication Critical patent/CN115895610A/en
Application granted granted Critical
Publication of CN115895610B publication Critical patent/CN115895610B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Abstract

The invention discloses a waterproof locking agent for drilling, which has the following structure:in the formula (I) of the present invention,is lignin, m is a natural number greater than 10, n is an integer from 0 to 6, X ‑ Is a monovalent anion; r is C 1 ～C 3 Alkyl or H.

Description

Waterproof locking agent for drilling well and preparation method and application thereof
Technical Field
The invention relates to the technical field of petroleum engineering, in particular to a waterproof locking agent for drilling and a preparation method and application thereof.
Background
In the drilling process, after the drilling fluid serving as an external fluid is in contact with the reservoir, the fluid retained in the microcrack cannot be completely discharged out of the stratum due to the existence of capillary force by the formation pressure, so that the water saturation of the reservoir is increased, the permeability of the oil and gas phase is reduced, and the phenomenon is called water-lock damage. At present, it is widely recognized in the industry that the primary causes of water lock damage are capillary self-priming and liquid phase retention. For low permeability reservoirs, water lock damage severely affects the capacity of the oil and gas resource. The addition of water-blocking agents to drilling fluids is the most straightforward method to inhibit or remove low permeability reservoir water-blocking damage. The waterproof locking agent is mainly used for removing reservoir water locking injury by increasing the contact angle between a liquid phase and the surface of rock, reducing the interfacial tension of a retention solution and accelerating the liquid drainage speed.
Currently, waterproof locking agents mainly comprise two major classes, namely surfactants and lower alcohols. The surfactant is used as waterproof locking agent to reduce the interfacial tension of liquid phase, change the wettability of rock surface and increase the wetting angle between liquid phase and rock surface, so as to reduce capillary resistance. The surfactant waterproof locking agent mainly comprises fluorocarbon surfactant, nonionic surfactant (polyoxyethylene polyoxypropylene glycol ether, alkylphenol polyoxyethylene ether, polyoxyethylene polyoxypropylene silanol ether), gemini surfactant and the like, and has the main reasons of slow dissolution speed, easy foaming and high cost, which prevent the large-scale application of the surfactant waterproof locking agent. The lower alcohol is used as a waterproof locking agent, and the alcohol can be mutually dissolved with water and is easy to volatilize, so that formation retention water can be brought out when the alcohol volatilizes. However, if the mineralization degree of the stratum water is high, lower alcohol is easy to cause alcohol precipitation, so that salt precipitation is caused, and micropores are blocked to cause irreversible reservoir pollution; in addition, when external water invades the reservoir again, the reservoir is damaged again due to the exhaustion of the alcohol waterproof locking agent.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a waterproof locking agent for drilling and a preparation method and application thereof, which aim to overcome the defects in the prior art, have good capabilities of reducing liquid phase interfacial tension and changing wettability of rock surfaces, have outstanding temperature resistance, salt resistance and solubility, have lower biotoxicity and biodegradability, and can be applied to development of oil and gas resources in environmentally sensitive areas.
The aim of the invention is achieved by the following technical scheme.
In a first aspect, the present invention provides a waterproof drilling locking agent having the following structure:
in the formula (I) of the present invention,lignin, m is a natural number greater than 10, n is a natural number from 0 to 6,
r is an alkyl group of 3 or less C or hydrogen.
In some embodiments, the natural number of m.ltoreq.18, preferably 11, 13, 15, 17.
In some embodiments, n is 2 or 3.
In some embodiments, the R is hydrogen.
In some embodiments, the X - Is BF 4 - 、PF 6 - 、SCN - 、HSO 3 - 、CH 3 SO 3 - 、 CF 3 SO 3 - 、CH 3 COO - 、CF 3 COO - 、Tf 2 N - 、CH 3 OSO 3 - 、C 2 H 5 OSO 3 - 、pTsO - 、 (CN) 2 N - 、CH 3 CH(OH)COO - 、F - 、Cl - 、Br - 、I - 、HCO 3 - One of them.
In some embodiments, the lignin is selected from sulfonated lignin, preferably one or more selected from sodium lignosulfonate, calcium lignosulfonate, potassium lignosulfonate, ammonium lignosulfonate, magnesium lignosulfonate, iron lignosulfonate, manganese lignosulfonate, and zinc lignosulfonate.
In some embodiments, the raw material obtained from the sulfonated lignin may be softwood, hardwood, and herbaceous plants, preferably softwood, hardwood.
In some embodiments, the sulfonated lignin has a molecular weight Mn: 2600-6000, mw:3200 to 7200.
It should be noted that, according to the present invention, since lignin generally has a large number of hydroxyl groups, aldehyde groups, etc., the structure shown in formula I only exemplarily shows the connection sequence and connection manner of the lignin and the cyano group-containing long carbon chain alkyl group, cyano group-containing imidazole ionic liquid, and does not mean that only one of the structures shown in formula I is connected to the ligninI.e. the number of groups attached is not limited.
In a second aspect, the invention provides a process for preparing a waterproof locking agent for drilling comprising reacting lignin with a cyano-substituted long-chain alkane of formula II, a cyano-containing imidazole ionic liquid of formula III in the presence of a solvent and a catalyst,
m is a natural number greater than 10, n is a natural number from 0 to 6,
r is an alkyl group having 3 or less carbon atoms or hydrogen.
In some embodiments, the natural number of m.ltoreq.18, preferably 11, 13, 15, 17.
In some embodiments, n is 2 or 3.
In some embodiments, the R is hydrogen.
In some embodiments, the X - Is BF 4 - 、PF 6 - 、SCN - 、HSO 3 - 、CH 3 SO 3 - 、 CF 3 SO 3 - 、CH 3 COO - 、CF 3 COO - 、Tf 2 N - 、CH 3 OSO 3 - 、C 2 H 5 OSO 3 - 、pTsO - 、 (CN) 2 N - 、CH 3 CH(OH)COO - 、F - 、Cl - 、Br - 、I - 、HCO 3 - One of them.
The preparation method of the waterproof locking agent for drilling provided by the invention comprises the following steps:
mixing lignin with long carbon chain alkyl containing cyano group shown in a formula II, imidazole ionic liquid containing cyano group shown in the formula II and a solvent;
heating, and adding a catalyst to react.
In some embodiments, lignin is first mixed with a solvent to form a mixed solution a; mixing the mixed solution A with long carbon chain alkyl containing cyano and imidazole ionic liquid containing cyano shown in the formulas II and II to form mixed solution B; then adding a catalyst into the mixed solution B after the mixture is added to a preset temperature under the protection of nitrogen, and reacting for a certain time to obtain a crude product of the waterproof locking agent.
In some embodiments, the solvent is selected from one or more of diethyl ether, propylene oxide, ethylene glycol ether, triethanolamine, acetone, butanone, methyl isobutyl ketone, carbon tetrachloride, chloroform, methylene chloride, 1-dichloroethane, 1, 2-dichloroethane, methyl ethyl ketone, tetrahydrofuran, petroleum ether, acetonitrile, ethyl acetate, benzene, toluene, m-xylene, chlorobenzene, cyclohexane, cyclohexanone, toluene cyclohexanone, methyl acetate, ethyl acetate, propyl acetate, nitromethane, 1, 4-dioxane, pyridine, morpholine, N-dimethylformamide, N-dimethylacetamide, and dimethylsulfoxide, preferably 1, 4-dioxane, pyridine, N-dimethylformamide, N-dimethylacetamide, and dimethylsulfoxide.
In some embodiments, the concentration of lignin in the solvent in the mixed solution a is 2.0wt% to 20.0wt%, preferably 6.0wt% to 12.0wt%.
In some embodiments, in mixed solution B, the mass of the cyano-containing long carbon chain alkyl is 2.0% to 12.0% of the lignin mass.
In some embodiments, in mixed solution B, the mass of the cyano-containing imidazole ionic liquid is 0.5% to 2.0% of the lignin mass.
In some embodiments, the catalyst isThe acid or Lewis acid is selected from sulfuric acid, phthalic acid imide, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, bismuth trifluoromethanesulfonic acid, calcium trifluoromethanesulfonic acid, copper trifluoromethanesulfonic acid, indium trifluoromethanesulfonic acid, bis-trifluoromethanesulfimide, boron trifluoride diethyl ether, perfluorosulfonic acid resin, 2, 4-dinitrobenzenesulfonic acid, dodecaphosphotungstic acid, and acid salt (Cs) of cesium phosphotungstate 2.5 H 0.5 PW 12 O 40 )、Cs 2 SO 4 、Ce(SO 4 ) 2 、P 2 O 5 、I 2 、CuCl、CuBr、CuI、CuCl 2 、 CoCl 2 、ZnCl 2 And FeCl 3 ·6H 2 O is preferably boron trifluoride, boron trifluoride diethyl ether, bismuth triflate, calcium triflate, copper triflate, indium triflate, perfluorosulfonic acid resin, cuCl 2 And FeCl 3 ·6H 2 O, more preferably boron trifluoride diethyl etherate, bismuth triflate, calcium triflate, copper triflate, indium triflate.
In some embodiments, the amount of the catalyst is 0.02% to 10.0%, preferably 0.5% to 8.0%, more preferably 2.0% to 7.0% of the total molar amount of the cyano-containing long carbon chain alkyl and cyano-containing imidazole ionic liquid.
In some embodiments, the temperature of the reaction is 80 to 160 ℃, preferably 90 to 150 ℃.
In some embodiments, the reaction time is 4 to 60 hours, preferably 8 to 56 hours, more preferably 16 to 48 hours.
The preparation method of the waterproof locking agent for drilling well, provided by the invention, further comprises the following steps: obtaining a crude product after the reaction is finished, and concentrating; soaking the crude product in ethanol, filtering, and washing.
In some embodiments, the washing is rinsing with acetone and glacial acetic acid-ethylene glycol at a volume ratio of 3:2, respectively.
In some embodiments, the soaking is for more than 24 hours, preferably more than 48 hours.
In some embodiments, drying is performed after the washing is completed, preferably freeze drying to constant weight.
In some embodiments, the concentration is by distillation under reduced pressure, preferably by rotary evaporation under reduced pressure.
In a third aspect, the present invention provides the use of a drilling water-repellent lock as described above, in some embodiments in the field of petroleum engineering, preferably by adding the water-repellent lock to a drilling fluid.
Compared with the prior art, the invention has the beneficial effects that:
(1) The waterproof locking agent for drilling provided by the invention is a natural modified product for realizing connection of lignin body and modified group through secondary amide group, has lower biotoxicity and biodegradability, and can be applied to development of oil and gas resources in environment-sensitive areas.
(2) Compared with the traditional surfactant waterproof locking agent, the waterproof locking agent for drilling fluid provided by the invention has the advantages that the long-carbon-chain alkyl containing cyano and the imidazole ionic liquid containing cyano are used for modifying lignin, and the waterproof locking agent has similar capabilities of reducing the interfacial tension of a liquid phase and changing the wettability of the surface of rock due to the introduction of the long-carbon-chain alkyl containing cyano and the imidazole ionic liquid containing cyano, but has outstanding temperature resistance, salt resistance and solubility, so that the waterproof locking agent plays a positive role in stabilizing the action effect of the waterproof locking agent under the conditions of high temperature and high mineralization.
Detailed Description
In order that the invention may be more readily understood, the invention will be described in detail below with reference to the following examples, which are given by way of illustration only and are not limiting of the scope of application of the invention.
Example 1
50g of potassium lignin sulfonate (source: poplar, mn:2600, mw: 3200) and 500g of N, N-dimethylformamide were charged into a reactor equipped with a temperature-controlling apparatus, a reflux condensing apparatus and a constant pressure charging apparatus, and after stirring sufficiently until dissolved, 3.6264g (0.02 mol) of dodecanitrile and 0.474g (0.002 mol) of 1-nitrile propyl-3-methylimidazole tetrafluoroborate were added. After nitrogen was introduced for 30 minutes, the temperature was raised to 92℃and 0.1561g (0.0011 mol) of boron trifluoride diethyl etherate was added thereto, followed by continuing the reaction under stirring for 36 hours.
After the reaction is finished, N-dimethylformamide is removed by reduced pressure distillation, the above products are put into ethanol solution, soaked for more than 24 hours, filtered, respectively sprayed with acetone and glacial acetic acid-glycol (volume ratio is 3:2), solid parts are taken, and freeze-dried to constant weight, thus obtaining the catalyst.
Example 2
Into a reactor equipped with a temperature-controlling device, a reflux condensing device and a constant pressure charging device, 60g of sodium lignin sulfonate (source: white oak, mn:3620, mw: 4275) and 800g of 1, 4-dioxane were charged, and after stirring sufficiently until dissolved, 2.0937g (0.01 mol) of tetradecanoic acid nitrile and 0.4322g (0.002 mol) of 1-nitriloethyl-3-methylimidazole bromide were added. After nitrogen was introduced for 30 minutes, the temperature was raised to 98℃and 0.1136g (0.0008 mol) of boron trifluoride diethyl etherate was added thereto, followed by continuing the reaction under stirring for 36 hours.
After the reaction is finished, distilling under reduced pressure to remove 1, 4-dioxane, putting the above product into ethanol solution, soaking for more than 24 hours, filtering, respectively using acetone and glacial acetic acid-ethylene glycol (volume ratio is 3:2) for showering, taking a solid part, and freeze-drying to constant weight to obtain the product.
Example 3
Into a reactor equipped with a temperature control device, a reflux condensing device and a constant pressure charging device, 100g of manganese lignin sulfonate (source: white pine, mn:6000, mw: 7180) and 800g of dimethyl sulfoxide were charged, and after stirring sufficiently until dissolved, 11.8712g (0.05 mol) of hexadecanoic acid nitrile and 1.9366g (0.0045 mol) of 1-nitrile propyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt were added. After nitrogen was introduced for 30 minutes, the temperature was raised to 125℃and 0.7234g (0.002 mol) of copper triflate was added thereto, followed by continuing the reaction for 28 hours with stirring.
After the reaction is finished, the dimethyl sulfoxide is distilled under reduced pressure, the products are put into ethanol solution, soaked for more than 24 hours, filtered, respectively sprayed by acetone and glacial acetic acid-glycol (volume ratio is 3:2), the solid part is taken, and the freeze-dried is carried out to constant weight, thus obtaining the product.
Example 4
Into a reactor equipped with a temperature control device, a reflux condensing device and a constant pressure charging device, 100g of calcium lignin sulfonate (source: korean pine, mn:5710, mw: 6400) and 1200g of pyridine were charged, after stirring sufficiently until dissolved, 10.6191g (0.04 mol) of octadecanitrile and 1.1807g (0.004 mol) of 1-nitrile propyl-3-methylimidazole hexafluorophosphate were added. After nitrogen was introduced for 30 minutes, the temperature was raised to 112℃and 0.7441g (0.0022 mol) of calcium triflate was added thereto, followed by continuing the reaction under stirring for 36 hours.
After the reaction is finished, decompressing and distilling to remove pyridine, putting the above products into ethanol solution, soaking for more than 24 hours, filtering, respectively using acetone and glacial acetic acid-ethylene glycol (volume ratio is 3:2) for showering, taking solid parts, and freeze-drying to constant weight to obtain the product.
Example 5
Into a reactor equipped with a temperature control device, a reflux condensing device and a constant pressure charging device, 100g of zinc lignin sulfonate (source: eucalyptus, mn:3240, mw: 3660) and 900g of N, N-dimethylacetamide were charged, after stirring sufficiently until dissolved, 10.879g (0.06 mol) of dodecanitrile and 1.4356g (0.006 mol) of 1-nitrile propyl-3-methylimidazole lactate were added. After nitrogen was introduced for 30 minutes, the temperature was raised to 150℃and 1.3124g (0.002 mol) of bismuth triflate was added thereto, followed by continuous reaction under stirring for 16 hours.
After the reaction is finished, N-dimethylacetamide is removed by reduced pressure distillation, the above products are put into ethanol solution, soaked for more than 24 hours, filtered, respectively sprayed with acetone and glacial acetic acid-glycol (volume ratio is 3:2), solid parts are taken, and freeze-dried to constant weight, thus obtaining the catalyst.
Example 6
Into a reactor equipped with a temperature control device, a reflux condensing device and a constant pressure charging device, 100g of iron lignin sulfonate (source: eucalyptus, mn:4780, mw: 5010) and 1500g of N, N-dimethylacetamide were charged, and after stirring sufficiently until dissolved, 3.6264g (0.02 mol) of dodecanitrile and 0.9555g (0.005 mol) of 1-nitrilethyl-3-methylimidazole thiocyanate salt were added. After nitrogen was introduced for 30 minutes, the temperature was raised to 145℃and 1.3124g (0.0017 mol) of indium triflate was added thereto, followed by continuous reaction under stirring for 24 hours.
After the reaction is finished, N-dimethylacetamide is removed by reduced pressure distillation, the above products are put into ethanol solution, soaked for more than 24 hours, filtered, respectively sprayed with acetone and glacial acetic acid-glycol (volume ratio is 3:2), solid parts are taken, and freeze-dried to constant weight, thus obtaining the catalyst.
Example 7
Into a reactor equipped with a temperature control device, a reflux condensing device and a constant pressure charging device, 100g of sodium lignin sulfonate (source: poplar, mn:5080, mw: 5330) and 760g of N, N-dimethylformamide were charged, and after stirring sufficiently until dissolved, 7.1227g (0.03 mol) of hexadecanoic acid nitrile and 0.5705g (0.002 mol) of 1-nitriloethyl-3-methylimidazole trifluoromethane sulfonate were added. After nitrogen was introduced for 30 minutes, the temperature was raised to 136℃and 0.7234g (0.002 mol) of copper triflate was added thereto, followed by continuing the reaction with stirring for 32 hours.
After the reaction is finished, N-dimethylformamide is removed by reduced pressure distillation, the above products are put into ethanol solution, soaked for more than 24 hours, filtered, respectively sprayed with acetone and glacial acetic acid-glycol (volume ratio is 3:2), solid parts are taken, and freeze-dried to constant weight, thus obtaining the catalyst.
Example 8
Into a reactor equipped with a temperature control device, a reflux condensing device and a constant pressure charging device, 100g of ammonium lignin sulfonate (source: eucalyptus, mn:3180, mw: 3460) and 1080g of N, N-dimethylacetamide were charged, and after stirring sufficiently until dissolved, 7.1227g (0.03 mol) of hexadecanoic acid nitrile and 0.9968g (0.004 mol) of 1-nitriloethyl-3-methylimidazole trifluoroacetate were added. After nitrogen was introduced for 30 minutes, the temperature was raised to 142℃and 0.7234g (0.002 mol) of copper triflate was added thereto, followed by continuing the reaction for 29.5 hours with stirring.
After the reaction is finished, N-dimethylacetamide is removed by reduced pressure distillation, the above products are put into ethanol solution, soaked for more than 24 hours, filtered, respectively sprayed with acetone and glacial acetic acid-glycol (volume ratio is 3:2), solid parts are taken, and freeze-dried to constant weight, thus obtaining the catalyst.
Example 9
Into a reactor equipped with a temperature-controlling device, a reflux condensing device and a constant pressure charging device, 120g of magnesium lignin sulfonate (source: masson pine, mn:6000, mw: 7200) and 1000g of N, N-dimethylacetamide were charged, and after stirring sufficiently until dissolution, 10.6191g (0.04 mol) of octadecyl nitrile and 1.5165g (0.005 mol) of diethyl 1-nitrile propyl-3-methylimidazole phosphate were added. After nitrogen was introduced for 30 minutes, the temperature was raised to 128℃and 1.085g (0.003 mol) of copper triflate was added thereto, followed by continuing the reaction for 44 hours with stirring.
After the reaction is finished, N-dimethylacetamide is removed by reduced pressure distillation, the above products are put into ethanol solution, soaked for more than 24 hours, filtered, respectively sprayed with acetone and glacial acetic acid-glycol (volume ratio is 3:2), solid parts are taken, and freeze-dried to constant weight, thus obtaining the catalyst.
Example 10
Into a reactor equipped with a temperature control device, a reflux condensing device and a constant pressure charging device, 100g of potassium lignin sulfonate (source: birch, mn:3200, mw: 3510) and 1000g of dimethyl sulfoxide were charged, and after stirring sufficiently until dissolved, 9.2917g (0.035 mol) of octadecanitrile and 1.607g (0.005 mol) of 1-nitrile propyl-3-methylimidazole p-toluenesulfonate were added. After nitrogen was introduced for 30 minutes, the temperature was raised to 132℃and 1.085g (0.003 mol) of copper triflate was added thereto, followed by continuous reaction under stirring for 48 hours.
After the reaction is finished, the dimethyl sulfoxide is distilled under reduced pressure, the products are put into ethanol solution, soaked for more than 24 hours, filtered, respectively sprayed by acetone and glacial acetic acid-glycol (volume ratio is 3:2), the solid part is taken, and the freeze-dried is carried out to constant weight, thus obtaining the product.
Example 11
Into a reactor equipped with a temperature control apparatus, a reflux condensing apparatus and a constant pressure charging apparatus, 100g of sodium lignin sulfonate (source: spruce, mn:5710, mw: 6000) and 1180g of N, N-dimethylacetamide were charged, and after stirring sufficiently until dissolved, 5.2343g (0.025 mol) of tetradecanoic acid and 1.2265g (0.005 mol) of 1-nitrile propyl-3-methylimidazole methanesulfonate were added. After nitrogen was introduced for 30 minutes, the temperature was raised to 120℃and 0.2839g (0.002 mol) of boron trifluoride diethyl etherate was added thereto, followed by continuous reaction under stirring for 46 hours.
After the reaction is finished, N-dimethylacetamide is removed by reduced pressure distillation, the above products are put into ethanol solution, soaked for more than 24 hours, filtered, respectively sprayed with acetone and glacial acetic acid-glycol (volume ratio is 3:2), solid parts are taken, and freeze-dried to constant weight, thus obtaining the catalyst.
Example 12
Into a reactor equipped with a temperature control apparatus, a reflux condensing apparatus and a constant pressure charging apparatus, 100g of calcium lignin sulfonate (source: eucalyptus, mn:4740, mw: 4980) and 960g of N, N-dimethylformamide were charged, and after stirring sufficiently until dissolved, 7.5374g (0.036 mol) of tetradecanecarbonitrile and 1.9782g (0.008 mol) of methyl 1-nitrilethyl-3-methylimidazole sulfate were added. After nitrogen was introduced for 30 minutes, the temperature was raised to 142℃and 1.9686g (0.003 mol) of bismuth triflate was added thereto, followed by continuous reaction under stirring for 24 hours.
After the reaction is finished, N-dimethylformamide is removed by reduced pressure distillation, the above products are put into ethanol solution, soaked for more than 24 hours, filtered, respectively sprayed with acetone and glacial acetic acid-glycol (volume ratio is 3:2), solid parts are taken, and freeze-dried to constant weight, thus obtaining the catalyst.
Comparative examples 1 to 12
The synthesis conditions of the prepared waterproof locking agent were kept the same as those of examples 1 to 12, respectively, except that no cyano group-containing imidazole ionic liquid was added.
Test example 1
C of modified lignin filtrate reducer molecule 9 Measurement of structural unit (phenylpropane structural unit), hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), and carbonyl group.
C 9 The method for measuring the structural unit is high performance liquid chromatography, and the specific operation program is from the following steps: chen Jun, zhao Fengxian, liu Xin, etc. high performance liquid chromatography for determining benzene content [ J ] in beverages]Beverage industry, 2009, 12 (10), 34-36;
the method for determining the total hydroxyl groups is an acetylation method, and the specific operation procedure is from: lang Weikuan, zhao Yingshu the acetylation method rapidly determines the hydroxyl content [ J ]. Chemical world, 1965,2, 57-58;
the method for measuring the phenolic hydroxyl group is Folin-Ciocalteu method, and the specific operation procedure is from: ainsworth E A, gillespie K.Estimation of total phenolic content and other oxidation substrates in plant tissues using Folin-Ciocalteu reagent [ J ]. Nature procls, 2017,2, 875-877;
the carbonyl group is determined by nuclear magnetic resonance, and the specific operation procedure is from: capanema E A, balakshin M Y, kadla J F.A comprehensive approach for quantitative lignin characterization by NMR spectroscopy [ J ]. Journal of Agricultural and Food Chemistry,2004, 52 (7), 1850-1860. The experimental results are shown in Table 1:
TABLE 1 preparation of lignin and products thereof of examples 1-12 functional group content (one/100C 9 Unit (C)
Note that: each sample was measured 5 times, averaged separately and taken as an integer.
As can be seen from comparing the numbers of the groups of examples 1 to 12 and the corresponding raw materials in table 1, the phenolic hydroxyl groups are unchanged before and after the reaction, and the numbers of the alcoholic hydroxyl groups and the carbonyl groups are remarkably reduced, so that the grafting reaction is mainly that the alcoholic hydroxyl groups and the carbonyl groups in lignin molecules are reacted; the number of the alcoholic hydroxyl groups and the carbonyl groups reacted in comparative examples 1 to 12 was relatively small compared to the number of the alcoholic hydroxyl groups and the carbonyl groups reacted in examples 1 to 12, which was mainly caused by the decrease in the number of the cyano group-containing graft monomers.
Test example 1: surface tension and interfacial tension test
The common surfactant type waterproof locking agent Sodium Dodecyl Sulfate (SDS), octyl phenol polyoxyethylene ether (OP-10), sorbitan monooleate (Span 80), sodium perfluorooctane sulfonate (PFOS), examples 1-12 and comparative examples 1-12 are selected to prepare aqueous solutions with the mass percent concentration of 0.4%, the aqueous solutions are aged for 16 hours at the temperature of 60 ℃, 100 ℃ and 140 ℃ respectively, and the surface tension and the interfacial tension of different waterproof locking agent solutions at the temperature of 25 ℃ are measured by means of a JYW-200C type full-automatic surface tension meter and a TX550A full-range interfacial tension meter, and experimental oil is island oil field pottery group crude oil. The experimental results are shown in tables 2 and 3:
TABLE 2 surface tension (mN/m) of waterproof locking agent under different temperature conditions
TABLE 3 interfacial tension (mN/m) of waterproof locking agent
/>
As can be seen from tables 2 and 3, examples 1 to 12 have lower surface tension and interfacial tension, comparable to PFOS, than SDS, OP-10 and Span80 after aging at 60 ℃; with the increase of aging temperature, the surface tension and interfacial tension of SDS, OP-10, span80, PFOS and comparative examples 1-12 are increased, while the trend of the increase of the surface tension and interfacial tension of examples 1-12 with the increase of temperature is obviously smaller, showing good temperature resistance, and can infer that the structural unit of the cyano-containing imidazole ionic liquid is introduced into lignin, so that the temperature resistance of the waterproof locking agent can be effectively improved.
Test example 2: evaluation of salt resistance
1.73g CaCl was added sequentially to 1000mL of water 2 、1.17gMgCl 2 、5.27gNa 2 SO 4 And 11.83g NaCl, stirred until completely dissolved to simulate formation water. Determination of the surface tension of SDS, OP-10, span80, PFOS, examples 1 to 12, comparative examples 1 to 5 at 0.4% by mass at Normal temperature 25℃in simulated formation WaterAnd interfacial tension, wherein the experimental oil is crude oil of a ceramic group in an island oil field. The experimental results are shown in table 4:
table 4 simulates the surface tension (mN/m) and interfacial tension (mN/m) of a waterproof locking agent in formation water
/>
As can be seen from table 4, in the simulated formation water, the surface tension and interfacial tension of examples 1 to 12 are significantly lower than those of SDS, OP-10, span80, PFOS and comparative examples 1 to 5, indicating that the salt-resistant effect of examples 1 to 12 is significantly better than that of conventional surfactant-type waterproof locking agents, and it can be inferred that the introduction of structural units of cyano-containing imidazole ionic liquid into lignin can effectively improve the salt-resistant ability of the waterproof locking agents.
Test example 3: evaluation of biotoxicity and biodegradability
The method for testing the biotoxicity of the drilling fluid mainly comprises the following steps: a biological detection method of the furfuryl shrimp, a microbial toxicity method and an accumulated biological fluorescence method. Of these, the shrimp bioassay is the only method formally approved by the U.S. Environmental Protection Agency (EPA) for evaluation of biological toxicity of drilling fluids. According to EPA-confirmed biotoxicity and organic pollutant biodegradability grading standard and test method, (biotoxicity grading standard: EC) 50 Less than or equal to 1, and extremely toxic; EC 1 < 50 Less than or equal to 100, high toxicity; EC of 100 < 50 Less than or equal to 1000, moderate toxicity; 1000 < EC 50 Less than or equal to 10000, slightly toxic; 10000 < EC 50 Less than or equal to 30000, and is nontoxic; EC (EC) 50 > 30000, recommended emission standard; biodegradability evaluation index (Y) = (biochemical oxygen demand (BOD)/Chemical Oxygen Demand (COD)). Times.100, Y is more than or equal to 25.0, and is easy to degrade; y is more than or equal to 15.0 and less than 25.0, and is easy to degrade; y is more than or equal to 5.0 and less than 15.0, and can be degraded; y is less than 5.0, and is difficult to degrade. ) The SDS, OP-10, span80, PFOS, examples 1 to 12 and comparative examples 1 to 12 were evaluated for biotoxicity and biodegradability, and the test results are shown in Table 5.
TABLE 5 biotoxicity and biodegradability of waterproof locking agents
Sample of EC 50 (mg/L) Y
SDS 27100 13.54
OP-10 27400 13.09
Span80 26600 12.57
PFOS 4500 6.25
Example 1 32000 29.46
Comparative example 1 32400 30.10
Example 2 36100 27.19
Comparative example 2 36600 27.28
Example 3 35000 28.08
Comparative example 3 35100 29.15
Example 4 34200 27.47
Comparative example 4 34500 27.90
Example 5 35300 28.00
Comparative example 5 35700 28.14
Example 6 35100 28.18
Comparative example 6 35300 28.42
Example 7 32900 28.37
Comparative example 7 33400 28.55
Example 8 32500 28.42
Comparative example 8 32600 28.75
Example 9 35200 26.97
Comparative example 9 35900 27.26
Example 10 34800 27.38
Comparative example 10 35200 27.91
Example 11 35100 28.14
Comparative example 11 35400 28.55
Example 12 33800 29.10
Comparative example 12 34200 29.47
As can be seen from Table 5, EC's of examples 1 to 12 and comparative examples 1 to 12 50 All higher than 30000mg/L, meets the emission standard, and the EC of SDS, OP-10 and Span80 50 Located at 10000 < EC 50 Less than or equal to 30000, achieves the nontoxic standard, and achieves the EC of PFOS 50 Located at 1000 < EC 50 Less than or equal to 10000, and shows slight toxicity. The Y values of examples 1 to 12 and comparative examples 1 to 12 are all higher than 25.0, and are easily degraded, so that the discharge standard is achieved, and the Y values of SDS, OP-10, span80 and PFOS are 5.0.ltoreq.Y < 15.0, so that the degradable standard is achieved. Experimental results show that compared with the conventional surfactant type waterproof locking agent, the waterproof locking agent obtained by taking lignin as a grafting matrix has good environmental protection.
The foregoing description is only illustrative of the preferred embodiments of the present invention and is not intended to limit the scope of the invention, which is defined broadly in the appended claims, and any person skilled in the art to which the invention pertains will readily appreciate that many modifications, including those that fall within the metes and bounds of the claims, or equivalence of such metes and bounds thereof.

Claims (12)

1. A waterproof drilling locking agent, which is characterized by comprising the following structure:
in the formula (I) of the present invention,is lignin, m is a natural number greater than 10 and less than 18, n is 2 or 3, X - For BF 4 - 、PF 6 - 、SCN - 、CH 3 SO 3 - 、CF 3 SO 3 - 、CH 3 COO - 、CF 3 COO - 、Tf 2 N - 、CH 3 OSO 3 - 、C 2 H 5 OSO 3 - 、(C 2 H 5 O) 2 PO 2 - 、TsO - 、CH 3 CH(OH)COO - 、F - 、Cl - 、Br - 、I - One of the following;
r is C 1 ～C 3 Alkyl or H.
2. The drilling waterproof lock agent according to claim 1, wherein m is 11, 13, 15, 17; and/or said R is H.
3. The waterproof drilling lock agent according to claim 1, wherein the lignin is selected from sulfonated lignin.
4. A drilling water lock agent according to claim 3, wherein the lignin is selected from one or more of sodium lignosulfonate, calcium lignosulfonate, potassium lignosulfonate, ammonium lignosulfonate, magnesium lignosulfonate, iron lignosulfonate, manganese lignosulfonate and zinc lignosulfonate.
5. A drilling water lock agent according to claim 3, wherein the sulphonated lignin is sulphonated lignin derived from softwood, hardwood or herbaceous plants.
6. The waterproof drilling locking agent according to claim 5, wherein the sulfonated lignin is a sulfonated lignin derived from softwood, hardwood.
7. A drilling waterproof locking agent according to claim 3, characterized in that the sulfonated lignin has a molecular weight Mn:2600 to 6000, and/or Mw:3200 to 7200.
8. The method for preparing a waterproof lock-out agent for well drilling according to any one of claims 1 to 7, wherein the method comprises reacting lignin with a cyano-substituted long-carbon alkane of formula II, a cyano-containing imidazole ionic liquid of formula III in the presence of a solvent and a catalyst,
m is a natural number greater than 10 and less than 18, n is 2 or 3, X - For BF 4 - 、PF 6 - 、SCN - 、CH 3 SO 3 - 、CF 3 SO 3 - 、CH 3 COO - 、CF 3 COO - 、Tf 2 N-、CH 3 OSO 3 - 、C 2 H 5 OSO 3 - 、(C 2 H 5 O) 2 PO 2 - 、TsO - 、CH 3 CH(OH)COO - 、F - 、Cl - 、Br - 、I - One of the following;
r is C 1 ～C 3 Alkyl or H.
9. The method of preparing a waterproof drilling lock agent according to claim 8, comprising:
mixing lignin with cyano-substituted long-carbon alkane shown in a formula II, cyano-containing imidazole ionic liquid shown in the formula II and a solvent;
heating, and adding a catalyst to react.
10. The method of preparing a waterproof drilling lock agent according to claim 8 or 9, further comprising:
obtaining a crude product after the reaction is finished, and concentrating; soaking the crude product in ethanol, filtering, and washing.
11. The method for preparing the waterproof locking agent for drilling according to claim 10, wherein the washing is carried out by respectively using acetone and glacial acetic acid-ethylene glycol with the volume ratio of 3:2.
12. Use of a drilling waterproof lock agent according to any one of claims 1-7 and/or obtained according to the method of preparation as claimed in claim 8.
CN202111165552.4A 2021-09-30 2021-09-30 Waterproof locking agent for drilling well and preparation method and application thereof Active CN115895610B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111165552.4A CN115895610B (en) 2021-09-30 2021-09-30 Waterproof locking agent for drilling well and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111165552.4A CN115895610B (en) 2021-09-30 2021-09-30 Waterproof locking agent for drilling well and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN115895610A CN115895610A (en) 2023-04-04
CN115895610B true CN115895610B (en) 2023-11-21

Family

ID=86490268

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111165552.4A Active CN115895610B (en) 2021-09-30 2021-09-30 Waterproof locking agent for drilling well and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN115895610B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012121828A1 (en) * 2011-03-09 2012-09-13 Baker Hughes Incorporated Well fluid and method of servicing a well
CN107418529A (en) * 2017-06-28 2017-12-01 常州明华运输有限公司 A kind of anti-caving agent for drilling fluid
CN108117866A (en) * 2016-11-30 2018-06-05 中国石油天然气股份有限公司 A kind of flushing fluid and preparation method thereof, application method and its assay method
CN110564381A (en) * 2019-09-28 2019-12-13 重庆威能钻井助剂有限公司 Composite filtrate reducer for drilling fluid and preparation method thereof
CN113429951A (en) * 2021-08-02 2021-09-24 浙江砉润科技有限公司 Biomass pollution-free oilfield blocking remover

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102887974B (en) * 2012-08-14 2014-06-04 蒋官澄 Anti-water-blocking agent for drilling fluid and preparation method thereof
US20150368540A1 (en) * 2014-06-19 2015-12-24 Api Intellectual Property Holdings, Llc Drilling fluid additives and fracturing fluid additives containing cellulose nanofibers and/or nanocrystals
CN105131913B (en) * 2015-02-11 2017-08-11 中国石油大学(北京) Reverse wetting agent and container horizon protective agent composition and its application suitable for hyposmosis ultra-low permeability reservoir

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012121828A1 (en) * 2011-03-09 2012-09-13 Baker Hughes Incorporated Well fluid and method of servicing a well
CN108117866A (en) * 2016-11-30 2018-06-05 中国石油天然气股份有限公司 A kind of flushing fluid and preparation method thereof, application method and its assay method
CN107418529A (en) * 2017-06-28 2017-12-01 常州明华运输有限公司 A kind of anti-caving agent for drilling fluid
CN110564381A (en) * 2019-09-28 2019-12-13 重庆威能钻井助剂有限公司 Composite filtrate reducer for drilling fluid and preparation method thereof
CN113429951A (en) * 2021-08-02 2021-09-24 浙江砉润科技有限公司 Biomass pollution-free oilfield blocking remover

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
An experimental study on the behaviors of new surfactant fracture fluid and its application in water lock gas reservoirs;Mou Shan-bo; Zhang Shi-cheng; Fu Dao-ming; Meng Qing-min; Sun Kan;Natural Gas Industry;第29卷(第12期);65-67 *
低渗油藏高压注水区块降压增注研究;赵贵林;中国优秀博硕学位论文全文数据库;第工程科技Ⅰ辑卷(第2015年第03期期);全文 *

Also Published As

Publication number Publication date
CN115895610A (en) 2023-04-04

Similar Documents

Publication Publication Date Title
CA1189303A (en) Method for recovering oil from sub-terranean deposits
JP2000516567A (en) Cement admixture that improves drying shrinkage
CN112226223A (en) Surfactant composition for pressure reduction and injection increase of ultra-low permeability oil reservoir and preparation method thereof
CN101955767B (en) Gemini surfactant for tertiary oil recovery chemical oil-displacing agent and preparation method thereof
CA1171778A (en) Method for recovering largely emulsion-free oil from underground deposits
CN108485627B (en) Preparation of clay anti-swelling agent with oil washing effect for water injection
CN115895610B (en) Waterproof locking agent for drilling well and preparation method and application thereof
CN108623926A (en) A kind of degradable synthetic rubber latex mulch and preparation method thereof
CN115386043A (en) Functional polyacrylamide and preparation method thereof
CN111073617A (en) Self-emulsifying blockage removing liquid and preparation method thereof
CN115521771A (en) Supermolecule-based environment-friendly foam scrubbing agent and application thereof
CN107540028B (en) Polysulfonate drilling waste harmless treatment agent and preparation method and application thereof
CN107686722A (en) A kind of oil resistant foam flooding finish and preparation method thereof, application
CN110698677B (en) Giant surfactant high-temperature foam stabilizer, foaming liquid, and preparation method and application thereof
CN112226222B (en) Low-tension viscoelastic surfactant composition for high-temperature high-mineralization oil reservoir chemical flooding tertiary oil recovery and preparation method thereof
CN115872892A (en) Well drilling waterproof locking agent monomer, well drilling waterproof locking agent, preparation method and application thereof
CN115028785A (en) Temperature-resistant salt-tolerant oil displacement surfactant and preparation method thereof
CN115434676A (en) Foam discharging agent for gas recovery of foam drainage of gas well and use method thereof
CN115651095B (en) Waterproof locking agent for drilling well and preparation method thereof
CN107383296A (en) A kind of cement water reducing agent and preparation method thereof
CN109679636B (en) Method for discharging liquid and gas production by adopting oil-resistant solid foam discharging agent composition
CN114479811A (en) Anionic-nonionic surfactant and preparation method and application thereof
CN113046047B (en) Preparation method of temperature-resistant surfactant for oil displacement
CN115368882B (en) Phase permeation regulator for oil field and preparation method thereof
CN114835849B (en) Salt-resistant antibacterial polyacrylamide for oil displacement and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant