CN104974265A - Etherification-modified konjac gum and preparation method thereof, water-base gel fracturing fluid containing the konjac gum and application thereof - Google Patents
Etherification-modified konjac gum and preparation method thereof, water-base gel fracturing fluid containing the konjac gum and application thereof Download PDFInfo
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Abstract
The invention discloses etherification-modified konjac gum which is prepared by performing etherification modification to substituted or non-substituted konjac gum, wherein the etherification modification can be single-anion etherification, multi-anion etherification, single-cation etherification, multi-cation etherification or anion-cation etherification. The invention provides a preparation of the etherification-modified konjac gum and also provides a water-base gel fracturing fluid containing the konjac gum and an application of the fracturing fluid in oil exploitation. The etherification-modified konjac gum is less in water-insoluble substances and is good in adhesivity. The water-base gel fracturing fluid with the konjac gum as a thickening agent is excellent in crosslinking performance and sand-carrying performance and is low in content of broken gum and residues.
Description
Technical field
The present invention relates to a kind of etherification modified konjak gum, and the preparation method of this etherification modified konjak gum, and containing as the water-base gel fracturing fluid of this etherification modified konjak gum of thickening material and the application of this fracturing liquid in oil production.
Background technology
Since the middle of last century, hydraulic fracturing technology is the Main Yield-increasing technology of domestic and international oil and gas development always.Enter the new millennium, the exploitation focus of world energy sources exploitation shifts to unconventional petroleum resources.Hydraulic fracturing technology, as the gordian technique of the unconventional developments of resources such as tight sand oil gas, coal-seam gas, shale oil gas, is paid much attention to.The fracturing fluid system of Low Damage, low cost is as ensureing pressing crack construction success and improving the key link of yield increase effect and extremely pay attention to.Aqueous fracturing fluid is primarily of compositions such as polymer viscosifier, linking agent, gel breaker, pH value regulator, sterilant, clay stabilizer and cleanup additives.Wherein thickening material is of the fracturing fluid basic additive, its effect is the viscosity improving water, reduces fluid loss, suspends and carry propping agent, therefore, the performance such as the water insoluble matter content of thickening material, tackifying ability, heatproof, anti-salt and shear resistant becomes and improves of the fracturing fluid research emphasis.
Melon glue and hydroxypropylation thereof or carboxymethylated derivative are the topmost thickening materials of aqueous fracturing fluid system.But the fast development due to the exploitation of planting area finite sum recent unconventionaloil pool Tibetan causes the lasting increase of demand, melon glue rapid rise of price.Except melon glue and derivative, domestic conventional vegetable jelly also has fenugreek gum, sesbania gum, soap benevolence glue and derivative thereof.Fenugreek gum is the main thickening material of the seventies pressure break in last century six, Technical comparing is ripe, possesses the condition of extensive rig-site utilization, but the nearly more than ten years are not applied in pressure break, to extensive for oil field compression fracture, there is limited source, the unmanageable problem of price equally.
But Amorphophallus Araeceae per nnial herb, have long plantation history in area, Southwestern China portion and central and west regions, output is higher.Konjak gum is the gluey polysaccharide of water-setting extracted from the stem tuber of various Amorphophallus konjac plant, is a kind of high molecular, non-ionic type glucomannan.Swollen profit after the particle chance water of Rhizoma amorphophalli powder, then breaks and discharges glucomannan polymkeric substance.The composition of konjak gum is similar to melon glue, and primarily of seminose and glucose composition, both mol ratios are about 1.6:1.But when natural konjak gum is as fracturing fluid thickener, its thickening property is poor and water insoluble matter content is more, and the property sheared is poor, is not easily cross-linked, broken glue difficulty.
In sum, this area lack a kind of instant, have that stronger tackifying ability, environmental friendliness, production cost are low, steady sources, constant product quality, performance are easy to regulate and control fracturing fluid thickener.
Summary of the invention
The object of the invention is to overcome the defect such as existing fracturing fluid thickener water insoluble matter content height and thickening property difference, provide etherification modified konjak gum that in a kind of water, dissolving power is comparatively strong and thickening property is stronger and preparation method thereof, and contain water-base gel fracturing fluid and the application of this fracturing liquid in oil production of this etherification modified konjak gum.
To achieve these goals, the invention provides a kind of etherification modified konjak gum, wherein, this etherification modified konjak gum is by substituted or unsubstituted konjak gum is carried out the etherification modified konjak gum obtained, wherein, described etherification modified be single anion etherificate, polyanionic etherificate, single positively charged ion etherificate, polycation etherificate or zwitterion etherificate.
Another object of the present invention is the preparation method providing a kind of described etherification modified konjak gum, the method comprises: undertaken etherification modified by substituted or unsubstituted konjak gum, wherein, described etherification modified be single anion etherificate, polyanionic etherificate, single positively charged ion etherificate, polycation etherificate or zwitterion etherificate.
Another object of the present invention is to provide a kind of water-base gel fracturing fluid, and this fracturing liquid contains above-mentioned etherification modified konjak gum.
Another object of the present invention is to provide the application of described water-base gel fracturing fluid in oil production.
Etherification modified konjak gum of the present invention is undertaken etherification modified by substituted or unsubstituted konjak gum and obtains, namely by after single anion etherificate, polyanionic etherificate, single positively charged ion etherificate, polycation etherificate or zwitterion etherificate, described substituted or unsubstituted konjak gum connection has been gone up and can have been strengthened water-soluble and group that is adhesion property.Therefore, by preparation method of the present invention, can obtain water-soluble better and the stronger konjak gum analogue of thickening property, can as thickening material in order to improve the overall performance of aqueous fracturing fluid, wherein, the water-base gel fracturing fluid containing this etherification modified konjak gum has that viscosity is high, friction resistance is little, thermotolerance advantages of higher, can take propping agent ability strong for oil production, after broken glue returns row simultaneously, level of residue is few, improves the quality of exploited crude oil.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of etherification modified konjak gum, wherein, this etherification modified konjak gum is by substituted or unsubstituted konjak gum is carried out the etherification modified konjak gum obtained, wherein, described etherification modified be single anion etherificate, polyanionic etherificate, single positively charged ion etherificate, polycation etherificate or zwitterion etherificate.
According to etherification modified konjak gum of the present invention, the substituting group of the konjak gum of described replacement is not particularly limited, and under preferable case, described substituting group is hydroxyalkyl, is more preferably C
1~ C
10hydroxyalkyl, be further preferably C
1~ C
6hydroxyalkyl.Further, described substituent substitution value is also not particularly limited, and under preferable case, described substituent substitution value is 0.1 ~ 0.55, is preferably 0.2 ~ 0.4.Abovementioned alkyl can be such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl, neo-pentyl, n-hexyl etc., therefore, above-mentioned hydroxyalkyl can be methylol, hydroxyethyl, hydroxypropyl, 2-hydroxyisopropyl, 4-hydroxy-n-butyl, 2-hydroxyisobutyl, 2-hydroxy tert-butyl, 5-hydroxyl n-pentyl, 4-hydroxyl isopentyl, 6-hydroxyl n-hexyl etc., is preferably hydroxypropyl.
The konjak gum that above-mentioned hydroxyalkyl replaces can be the commercially available product bought from company, and preparation method's synthesis of the konjak gum that also can be replaced by the preferred hydroxyalkyl of the present invention is obtained, and the method comprises: contacted with epoxy haloalkane by unsubstituted konjak gum.In this preparation method, described epoxy haloalkane can be selected as required, such as, can be one or more in epoxy chloropropane, epoxy chlorobutane, epoxy bromopropane and epoxy n-butyl bromide.Catalytic solvent in above-mentioned preparation method can be Virahol and/or acetone.The reaction conditions of described contact is: under normal pressure, and temperature of reaction is 30-90 DEG C, and the reaction times is 2-5 hour.
According to etherification modified konjak gum of the present invention, described etherification modified konjak gum is obtained substituted or unsubstituted konjak gum and ion etherifying agent generation etherification reaction, described etherification reaction can be the reaction of any one hydroxyl in described ion etherifying agent and konjak gum structure, under preferable case, the primary hydroxyl generation etherification reaction of 6 carbon atoms of the glucose on described ion etherifying agent and konjak gum main chain.Above-mentioned etherification reaction makes this substituted or unsubstituted konjak gum connect the ion Etherifying groups that can improve performance when konjak gum uses as thickening material.The ion etherificate substitution value of described ion Etherifying groups determined by the hydroxyl value be substituted in the repeating unit of average each konjak gum main chain, and under preferable case, described ion etherificate substitution value is 0.01-1.5, is more preferably 0.15-0.55.
According to etherification modified konjak gum of the present invention, described single anion etherificate is that the etherification modified konjak gum obtained only has single negatively charged ion Etherifying groups by substituted or unsubstituted konjak gum and a kind of negatively charged ion etherifying agent contact reacts.Particularly, the process of described single anion etherificate can comprise: in the basic conditions, by substituted or unsubstituted konjak gum and negatively charged ion etherifying agent contact reacts.Wherein, described negatively charged ion etherifying agent can form negatively charged ion for being dissolved in the water and formed negatively charged ion can with the reagent of the various routines of hydroxyl generation etherification reaction, be preferably carboxylate salt, sulfonate, sulfuric acid or phosphate ester salt, be more preferably sodium chloroacetate, chloroethyl sodium sulfonate, the chloro-2-hydroxypropyl azochlorosulfonate acid sodium of 3-or epoxypropyl sodium sulfonate.
According to etherification modified konjak gum of the present invention, described polyanionic etherificate be by substituted or unsubstituted konjak gum successively with multiple negatively charged ion etherifying agent or simultaneously with the mixture contact reacts of multiple negatively charged ion etherifying agent, the etherification modified konjak gum obtained has two or more negatively charged ion Etherifying groups.Under preferable case, the process of described polyanionic etherificate comprises: in the basic conditions, by substituted or unsubstituted konjak gum successively with multiple negatively charged ion etherifying agent contact reacts.Wherein, described negatively charged ion etherifying agent can form negatively charged ion for being dissolved in the water and the negatively charged ion formed can with one or more in the reagent of the various routines of hydroxyl generation etherification reaction, be preferably in carboxylate salt, sulfonate, sulfuric acid and phosphate ester salt one or more, be more preferably in sodium chloroacetate, chloroethyl sodium sulfonate, the chloro-2-hydroxypropyl azochlorosulfonate acid sodium of 3-and epoxypropyl sodium sulfonate one or more.
According to etherification modified konjak gum of the present invention, described single positively charged ion etherificate is that the etherification modified konjak gum obtained only has single positively charged ion Etherifying groups by substituted or unsubstituted konjak gum and a kind of cationic etherifying agent contact reacts.Particularly, the process of described single positively charged ion etherificate can comprise: in the basic conditions, by substituted or unsubstituted konjak gum and cationic etherifying agent contact reacts.Wherein, described cationic etherifying agent can be with can with the various conventional reagent of the cation group of hydroxyl generation etherification reaction, be preferably tertiary ammonium salt or quaternary ammonium salt, be more preferably dimethylamino monochloroethane hydrochloride, dimethylamino chloropropane hydrochloride, dimethylamino chlorobutane hydrochloride, diethylin monochloroethane hydrochloride, diethylamino chloropropane hydrochloride, diethylamino chlorobutane hydrochloride, epoxypropyl dimethyl hexadecyl ammonium chloride or 3-chloro-2-hydroxypropyl dimethyl cetyl chloride ammonium.
According to etherification modified konjak gum of the present invention, described polycation etherificate be by substituted or unsubstituted konjak gum successively with multiple cationic etherifying agent or simultaneously with the mixture contact reacts of multiple cationic etherifying agent, the etherification modified konjak gum obtained has two or more positively charged ion Etherifying groups.Under preferable case, the process of described polycation etherificate can comprise: in the basic conditions, by substituted or unsubstituted konjak gum successively with multiple cationic etherifying agent contact reacts.Wherein, described cationic etherifying agent be with can with one or more in the various conventional reagent of the cation group of hydroxyl generation etherification reaction, be preferably in tertiary ammonium salt and quaternary ammonium salt one or more, be more preferably dimethylamino monochloroethane hydrochloride, dimethylamino chloropropane hydrochloride, dimethylamino chlorobutane hydrochloride, diethylin monochloroethane hydrochloride, diethylamino chloropropane hydrochloride, diethylamino chlorobutane hydrochloride, one or more in epoxypropyl dimethyl hexadecyl ammonium chloride and 3-chloro-2-hydroxypropyl dimethyl cetyl chloride ammonium.
According to etherification modified konjak gum of the present invention, described zwitterion etherificate be by substituted or unsubstituted konjak gum first with negatively charged ion etherifying agent contact reacts, then with cationic etherifying agent contact reacts; Or substituted or unsubstituted konjak gum is direct and negatively charged ion etherifying agent and cationic etherifying agent mixture contact reacts.Under preferable case, the process of described zwitterion etherificate comprises: in the basic conditions, by substituted or unsubstituted konjak gum first with negatively charged ion etherifying agent contact reacts, then with cationic etherifying agent contact reacts.Wherein, described negatively charged ion etherifying agent can form negatively charged ion for being dissolved in the water and the negatively charged ion formed can with one or more in the reagent of the various routines of hydroxyl generation etherification reaction, be preferably in carboxylate salt, sulfonate, sulfuric acid and phosphate ester salt one or more, be more preferably in sodium chloroacetate, chloroethyl sodium sulfonate, the chloro-2-hydroxypropyl azochlorosulfonate acid sodium of 3-and epoxypropyl sodium sulfonate one or more.Described cationic etherifying agent can be with can with one or more in the various conventional reagent of the cation group of hydroxyl generation etherification reaction, be preferably in tertiary ammonium salt and quaternary ammonium salt one or more, be more preferably in dimethylamino monochloroethane hydrochloride, dimethylamino chloropropane hydrochloride, dimethylamino chlorobutane hydrochloride, diethylin monochloroethane hydrochloride, diethylamino chloropropane hydrochloride, diethylamino chlorobutane hydrochloride, epoxypropyl dimethyl hexadecyl ammonium chloride and 3-chloro-2-hydroxypropyl dimethyl cetyl chloride ammonium one or more.In preferred situation, the process of described zwitterion etherificate comprises: in the basic conditions, by substituted or unsubstituted konjak gum first with a kind of negatively charged ion etherifying agent contact reacts, then with a kind of cationic etherifying agent contact reacts.Wherein, described negatively charged ion etherifying agent and described cationic etherifying agent are selected from the above-mentioned kind enumerated separately.
Present invention also offers a kind of preparation method of etherification modified konjak gum, the method comprises: undertaken etherification modified by substituted or unsubstituted konjak gum, wherein, described etherification modified be single anion etherificate, polyanionic etherificate, single positively charged ion etherificate, polycation etherificate or zwitterion etherificate.
In the above-mentioned methods, described substituted or unsubstituted konjak gum with describe above identical.
In the above-mentioned methods, described single anion etherificate, described polyanionic etherificate, described single positively charged ion etherificate, described polycation etherificate and described zwitterion etherificate can be implemented according to the method described above.Under preferable case, described etherification modified process comprises: be dissolved in solvent by substituted or unsubstituted konjak gum, then adds alkali and etherifying agent (i.e. negatively charged ion etherifying agent and/or cationic etherifying agent) wherein, and temperature reaction.Wherein, the weight ratio of the consumption of described substituted or unsubstituted konjak gum, solvent, alkali and etherifying agent is preferably 100:(500 ~ 700): (2 ~ 40): (1 ~ 60), is more preferably 100:(550 ~ 650): (5 ~ 15): (12 ~ 40).When described etherification modified process is carried out repeatedly, in aforementioned proportion scope, the consumption of etherifying agent refers to the consumption of etherifying agent in each etherification modified process.Described alkali and etherifying agent can add reaction system with the form of its aqueous solution.When described alkali and etherifying agent add fashionable in form of an aqueous solutions, the weight ratio of described substituted or unsubstituted konjak gum and water can be 100:(15 ~ 150), be preferably 100:(30 ~ 80).
The kind of described solvent is not particularly limited, as long as can dissolve substituted or unsubstituted konjak gum, under preferable case, described solvent is Virahol and/or acetone.
The kind of described alkali is not particularly limited, as long as can maintain reaction soln is basic solution, under preferable case, described alkali is one or more in sodium hydroxide, potassium hydroxide and lithium hydroxide.
In the above-mentioned methods, described etherification modified condition optimization makes the ion etherificate substitution value of described etherification modified konjak gum be 0.01-1.5, is more preferably 0.15-0.55.Particularly, described etherification modified condition can comprise: temperature of reaction is 40-90 DEG C, preferred 50-80 DEG C; Reaction times is 2-4h, is preferably 2.5-3.5h.
In one more preferably embodiment, described etherification modified process comprises: under agitation, substituted or unsubstituted konjak gum is dissolved in solvent, and pass into inactive gas in stirring and dissolving process, alkaline solution is added after 20-40min, etherifying agent (i.e. negatively charged ion etherifying agent and/or cationic etherifying agent) is added, temperature reaction subsequently after 20-40min.Wherein, described inactive gas can be any gas do not reacted with reaction soln, is preferably at least one in nitrogen, argon gas and neon, is more preferably nitrogen.The temperature of described intensification is preferably 40-90 DEG C, is more preferably 50-80 DEG C.The time of described reaction is preferably 2-4h, is more preferably 2.5-3.5h.
Method of the present invention can also comprise after the completion of reaction, neutralizes with the mixture of acid to gained.The kind of described acid is not particularly limited, and under preferable case, described acid is one or more in hydrochloric acid, phosphoric acid, citric acid and acetic acid.
Present invention also offers a kind of water-base gel fracturing fluid, this fracturing liquid contains above-mentioned etherification modified konjak gum.
Be cross-linked to make etherification modified konjak gum, obtain above-mentioned water-base gel fracturing fluid, this fracturing liquid is also containing linking agent, described linking agent can be the linking agent that can be cross-linked konjak gum of this area routine, such as dicumyl peroxide (DCP), potent type aziridine crosslinker SAC-100, organic zirconium crosslinker YBJ-3, organic titanium cross-linking agent TYZOR TE, one or more in linking agent TAIC etc., and the consumption of this linking agent can decide according to the of the fracturing fluid intensity of different oil production environments need and viscosity, such as, relative to of the fracturing fluid gross weight, the content of described linking agent can be 1-15 % by weight.
Above-mentioned water-base gel fracturing fluid can also contain the additive of this area routine, such as expansion-resisting agent, cleanup additive, alkali etc., wherein, described expansion-resisting agent, described cleanup additive and described alkali can for ability routine can be added into of the fracturing fluid additive, its consumption can adjust as required accordingly, repeats no more here.
A preferred embodiment of the invention, described water-base gel fracturing fluid is by described etherification modified konjak gum, linking agent, alkali, expansion-resisting agent and cleanup additive is soluble in water obtains, wherein, relative to the water of 100 weight parts, the content of described etherification modified konjak gum, linking agent, alkali, expansion-resisting agent and cleanup additive is respectively 1-0.1 weight part, 0.6-0.05 weight part, 0.6-0.05 weight part, 1.2-0.2 weight part and 1.2-0.2 weight part.Described linking agent can be such as dicumyl peroxide (DCP), potent type aziridine crosslinker SAC-100, organic zirconium crosslinker YBJ-3, organic titanium cross-linking agent TYZOR TE, one or more in linking agent TAIC etc., described alkali can be such as sodium hydroxide, potassium hydroxide, one or more in calcium hydroxide etc., described expansion-resisting agent can be such as Repone K, quaternary surfactant, polyamine, one or more in poly-quaternary amine etc., described cleanup additive can be such as fluorine carbon cleanup additive FC-117, oxyethyl group modification gathers trisiloxanes cleanup additive BD-3078, one or more in Gemini surface active cleanup additive BA1-5 etc.
Present invention also offers the application of above-mentioned aqueous fracturing fluid in oil production.
Below will be described the present invention by embodiment.
In following test case, the limiting viscosity of polymkeric substance measures according to the method in GB/T12005.1-89 " polyacrylamide characteristic viscosity determining method ";
Solid content measures according to the method in GB/T12005.2-1989 " polyacrylamide determination of solid content method ";
Dissolution time measures according to the method specified in petroleum exploration and development research institute of Henan Oil Field branch office experimental center job instruction Q/HNYJ325-2007;
Water insoluble matter content measures according to the method in GB/T9738-2008 " chemical reagent-water insoluble substance determination universal method ";
Base fluid apparent viscosity measures according to the method in SY/T5764-2007 " pressure break vegetable jelly generic specifications ";
Viscosity-average molecular weight is according to formula M
v=([η]/K)
1/ α, wherein K=4.5 × 10
-3, α=0.80 calculates;
Ion etherificate substitution value is the deuterated water dissolution by being used by sample containing 10% deuterated hydrochloric acid, and with after being hydrolyzed half an hour in 70 DEG C of heating in water bath situations, the method that nuclear magnetic resonance spectrometer carries out hydrogen spectrum analysis measures, its method of calculation are: utilize characteristic group in substituting group (as carboxymethyl methylene, the proton etc. of the methyl in the methylene radical be directly connected with sulfonic group in sulfonic group and hydroxypropyl dimethyl cetyl chloride ammonium on hexadecyl) peak integral area and konjak gum chain on semi-lactosi or the peak integral area of seminose anomeric proton (selection and the integral area size needs at this peak are determined according to the structure of concrete konjak gum, here peak integral area represents the quantity of the structural unit of this concrete konjak gum in a word) ratio to calculate the substitution value of each ion etherifying agent, namely obtain on the structural unit on average each konjak gum chain, by the number of the hydroxyl that etherificate replaces,
Cold cross-linking performance and broken glue residue content measure according to the method in SY/T5107-2005 " aqueous fracturing fluid method of evaluating performance ";
Normal temperature takes the measuring method of grittiness energy: prior to adding appropriate fracturing liquid in graduated cylinder, then taking 10g propping agent and being placed on liquid level, leaves standstill 12h and observes sedimentation situation; Of the fracturing fluid viscosity is measured with Brookfield viscometer.
Konjak gum (sticky equal molecular mass 2,850,000 gmol in following examples
-1) purchased from company of permanent Chemicals company limited of Zhengzhou City one, chloroethyl sodium sulfonate is purchased from Tianjin Heowns Biochemical Technology Co., Ltd., N, N-diethyl chloroethylamine hydrochloride and the chloro-2-hydroxypropyl-trimethyl ammonium chloride of 3-are purchased from Shanghai Mai Ruier chemical technology company limited, organic zirconium crosslinker YBJ-3 is purchased from Xi'an Ya Bang Petroleum Technology Co., Ltd, fluorine carbon cleanup additive FC-117 purchased from Shanghai Jian Hong Industrial Co., Ltd., Bruker company of the specification Switzerland AVANCE300MHz of nuclear-magnetism instrument.
Preparation example 1
This preparation example is for illustration of the preparation method of hydroxypropyl konjac glucomannan.
100kg konjak gum is dissolved in 650L Virahol, logical nitrogen 30min, adds the aqueous solution of the sodium hydroxide of 20 % by weight of 35kg at temperature is 20 DEG C, adds the ethanolic soln of the epoxy chloropropane of 25 % by weight of 35kg after stirring 30min again, be warming up to 80 DEG C, reaction 4h.After reaction terminates, neutralize with acetic acid, filter, washing, dry, pulverize, obtain 96kg hydroxypropyl konjac glucomannan A, viscosity-average molecular weight is 2,910,000 gmol
-1, the substitution value of hydroxypropyl is 0.32.
Embodiment 1
The present embodiment is for illustration of described etherification modified konjak gum provided by the invention and preparation method thereof.
Hydroxypropyl konjac glucomannan A in 100kg preparation example 1 is dissolved in 650L Virahol, logical nitrogen 30min, adds the aqueous solution of the sodium hydroxide of 20 % by weight of 32kg at temperature is 20 DEG C, adds the aqueous solution of the sodium chloroacetate of 75 % by weight of 35kg after stirring 30min, be warming up to 75 DEG C, reaction 3h.After reaction terminates, neutralize with citric acid, filter, washing, dry, pulverize, obtain 94kg carboxy-methyl hydroxy propyl konjak gum A1.
Embodiment 2
The present embodiment is for illustration of described etherification modified konjak gum provided by the invention and preparation method thereof.
Hydroxypropyl konjac glucomannan A in 100kg preparation example 1 is dissolved in 650L Virahol, logical nitrogen 30min, the aqueous solution of the sodium hydroxide of 20 % by weight of 32kg is added at temperature is 20 DEG C, the aqueous solution of the chloroethyl sodium sulfonate of 25 % by weight of 32kg is added again after stirring 30min, be warming up to 80 DEG C, reaction 4h.After reaction terminates, neutralize with acetic acid, filter, washing, dry, pulverize, obtain 95kg sulfoethyl hydroxypropyl konjac glucomannan A2.
Embodiment 3
The present embodiment is for illustration of described etherification modified konjak gum provided by the invention and preparation method thereof.
The product A 1 of 100kg embodiment 1 is dissolved in 600L Virahol, logical nitrogen 30min, adds the aqueous solution of the sodium hydroxide of 20 % by weight of 32kg at temperature is 20 DEG C, adds the aqueous solution of the chloroethyl sodium sulfonate of 25 % by weight of 32kg after stirring 30min again, be warming up to 80 DEG C, reaction 4h.After reaction terminates, neutralize with citric acid, filter, washing, dry, pulverize, obtain 96kg sulfoethyl carboxy-methyl hydroxy propyl konjak gum A3.
Embodiment 4
The present embodiment is for illustration of described etherification modified konjak gum provided by the invention and preparation method thereof.
The product A 1 of 100kg embodiment 1 is dissolved in 550L acetone, logical nitrogen 30min, the aqueous solution of the sodium hydroxide of 30 % by weight of 30kg is added at temperature is 20 DEG C, the N of 27 % by weight of 60kg is added again after stirring 30min, the aqueous solution of N-diethyl chloroethylamine hydrochloride, be warming up to 50 DEG C, reaction 3h.After reaction terminates, neutralize with citric acid, filter, washing, dry, pulverize, obtain 93kg N, N-diethyl ethanamine base carboxy-methyl hydroxy propyl konjak gum A4.
Embodiment 5
The present embodiment is for illustration of described etherification modified konjak gum provided by the invention and preparation method thereof.
The product A 1 of 100kg embodiment 1 is dissolved in 600L acetone, logical nitrogen 30min, the aqueous solution of the sodium hydroxide of 20 % by weight of 45kg is added at temperature is 20 DEG C, the aqueous solution of the chloro-2-hydroxypropyl-trimethyl ammonium chloride of 3-of 50 % by weight of 80kg is added again after stirring 30min, be warming up to 50 DEG C, reaction 3h.After reaction terminates, neutralize with lemon acetic acid, filter, washing, dry, pulverize, obtain the chloro-2-hydroxypropyl of 94kg3--trimethylammonium ammonium carboxy-methyl hydroxy propyl konjak gum A5.
Embodiment 6
The present embodiment is for illustration of described etherification modified konjak gum provided by the invention and preparation method thereof.
The product A 2 of 100kg embodiment 2 is dissolved in 550L acetone, logical nitrogen 30min, the aqueous solution of the sodium hydroxide of 30 % by weight of 30kg is added at temperature is 20 DEG C, the N of 27 % by weight of 60kg is added again after stirring 30min, the aqueous solution of N-diethyl chloroethylamine hydrochloride, be warming up to 50 DEG C, reaction 3h.After reaction terminates, neutralize with acetic acid, filter, washing, dry, pulverize, obtain 96kg N, N-diethyl ethylamino sulfoethyl hydroxypropyl konjac glucomannan A6.
Embodiment 7
The present embodiment is for illustration of described etherification modified konjak gum provided by the invention and preparation method thereof.
According to the method for embodiment 1, unlike, add 100kg konjak gum and replace hydroxypropyl konjac glucomannan A, obtain 94kg carboxy methyl konjaku glue A7.
Embodiment 8
The present embodiment is for illustration of described etherification modified konjak gum provided by the invention and preparation method thereof.
Method according to embodiment 4, unlike, add 100kg hydroxypropyl konjac glucomannan A and replace A1, obtain 95kg N, N-diethyl ethylamino hydroxypropyl konjac glucomannan A8.
Embodiment 9
The present embodiment is for illustration of described etherification modified konjak gum provided by the invention and preparation method thereof.
Method according to embodiment 5, unlike, the product A 8 adding 100kg embodiment 8 replaces A1, obtains 94kg3-chloro-2-hydroxypropyl-trimethylammonium ammonium-N, N-diethyl chloroethene ammonium hydroxypropyl konjac glucomannan A9.
Application Example 1
The present embodiment is for illustration of water-base gel fracturing fluid of the present invention.
The product A 1-A9 of embodiment 1-9 and konjak gum are respectively taken 250g water-soluble, add 200g organic zirconium crosslinker YBJ-3,200g sodium hydroxide, 300g Repone K and 300g fluorine carbon cleanup additive FC-117 more respectively, be uniformly mixed, namely obtain the water-base gel fracturing fluid that 100kg contains the thickening material of above-mentioned different konjak gum.
Test case 1
Respectively to the product A 1-A9 in embodiment 1-9 do nucleus magnetic hydrogen spectrum (
1h-NMR), and its hydrogen spectrum is analyzed, calculate ion etherificate substitution value; Measure the viscosity-average molecular weight of the product A 1-A9 in embodiment 1-9 and konjak gum, solid content, dissolution time, water insoluble matter content, base fluid apparent viscosity and limiting viscosity respectively, measurement result is as shown in table 1; Cold cross-linking performance is carried out to the corresponding water-base gel fracturing fluid obtained in Application Example 1 simultaneously, normal temperature takes grittiness energy and the mensuration of broken glue residue content, wherein, cold cross-linking performance measurement result shows that the water-base gel fracturing fluid prepared in Application Example 1 is crosslinked and can hang, normal temperature takes the water-base gel fracturing fluid that grittiness energy measurement result shows to prepare in Application Example 1 can take sand, and its broken glue residue content measurement result is in shown in konjak gum field corresponding in table 1.
Table 1
From table 1, the data of contrast A1-A9 and konjak gum can be found out, the molecular weight of the konjak gum after etherification modified increases all to some extent, in water, dissolution time is shorter simultaneously, better water-soluble, water-insoluble is less, and apparent viscosity is higher, the water-base gel fracturing fluid obtained for thickening material has good cross-linking properties and takes grittiness energy, and broken glue residue content is lower.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (16)
1. an etherification modified konjak gum, it is characterized in that, this etherification modified konjak gum is by substituted or unsubstituted konjak gum is carried out the etherification modified konjak gum obtained, wherein, described etherification modified be single anion etherificate, polyanionic etherificate, single positively charged ion etherificate, polycation etherificate or zwitterion etherificate.
2. konjak gum according to claim 1, wherein, the substituted radical in the konjak gum of described replacement is C
1~ C
10hydroxyalkyl, be preferably C
1~ C
6hydroxyalkyl; And the substitution value of described substituted radical is 0.1-0.55, be preferably 0.2-0.4.
3. konjak gum according to claim 1, wherein, the ion etherificate substitution value of described etherification modified konjak gum is 0.01-1.5, is preferably 0.15-0.55.
4. konjak gum according to claim 1, wherein, described single anion etherification procedure comprises: in the basic conditions, by substituted or unsubstituted konjak gum and negatively charged ion etherifying agent contact reacts, wherein, described negatively charged ion etherifying agent is carboxylate salt, sulfonate, sulfuric acid or phosphate ester salt, is preferably sodium chloroacetate, chloroethyl sodium sulfonate, the chloro-2-hydroxypropyl azochlorosulfonate acid sodium of 3-or epoxypropyl sodium sulfonate.
5. konjak gum according to claim 1, wherein, the process of described polyanionic etherificate comprises: in the basic conditions, by substituted or unsubstituted konjak gum successively with multiple negatively charged ion etherifying agent contact reacts, wherein, various described negatively charged ion etherifying agent is one or more in carboxylate salt, sulfonate, sulfuric acid and phosphate ester salt separately, is preferably one or more in sodium chloroacetate, chloroethyl sodium sulfonate, the chloro-2-hydroxypropyl azochlorosulfonate acid sodium of 3-and epoxypropyl sodium sulfonate.
6. konjak gum according to claim 1, wherein, the process of described single positively charged ion etherificate comprises: in the basic conditions, by substituted or unsubstituted konjak gum and cationic etherifying agent contact reacts, wherein, described cationic etherifying agent is tertiary ammonium salt or quaternary ammonium salt, be preferably dimethylamino monochloroethane hydrochloride, dimethylamino chloropropane hydrochloride, dimethylamino chlorobutane hydrochloride, diethylin monochloroethane hydrochloride, diethylamino chloropropane hydrochloride, diethylamino chlorobutane hydrochloride, epoxypropyl dimethyl hexadecyl ammonium chloride or 3-chloro-2-hydroxypropyl dimethyl cetyl chloride ammonium.
7. konjak gum according to claim 1, wherein, the process of described polycation etherificate comprises: in the basic conditions, by substituted or unsubstituted konjak gum successively with multiple cationic etherifying agent contact reacts, wherein, various described cationic etherifying agent is one or more in tertiary ammonium salt and quaternary ammonium salt separately, be preferably dimethylamino monochloroethane hydrochloride, dimethylamino chloropropane hydrochloride, dimethylamino chlorobutane hydrochloride, diethylin monochloroethane hydrochloride, diethylamino chloropropane hydrochloride, diethylamino chlorobutane hydrochloride, one or more in epoxypropyltrimethylchloride chloride and 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride.
8. konjak gum according to claim 1, wherein, the process of described zwitterion etherificate comprises: in the basic conditions, first and the negatively charged ion etherifying agent contact reacts by substituted or unsubstituted konjak gum, again with cationic etherifying agent contact reacts, wherein, described negatively charged ion etherifying agent is one or more in carboxylate salt, sulfonate, sulfuric acid and phosphate ester salt, is preferably one or more in sodium chloroacetate, chloroethyl sodium sulfonate, the chloro-2-hydroxypropyl azochlorosulfonate acid sodium of 3-and epoxypropyl sodium sulfonate; Described cationic etherifying agent is one or more in tertiary ammonium salt and quaternary ammonium salt, is preferably one or more in dimethylamino monochloroethane hydrochloride, dimethylamino chloropropane hydrochloride, dimethylamino chlorobutane hydrochloride, diethylin monochloroethane hydrochloride, diethylamino chloropropane hydrochloride, diethylamino chlorobutane hydrochloride, epoxypropyl dimethyl hexadecyl ammonium chloride and 3-chloro-2-hydroxypropyl dimethyl cetyl chloride ammonium.
9. the preparation method of an etherification modified konjak gum, the method comprises: undertaken etherification modified by substituted or unsubstituted konjak gum, wherein, described etherification modified be single anion etherificate, polyanionic etherificate, single positively charged ion etherificate, polycation etherificate or zwitterion etherificate.
10. method according to claim 9, wherein, the substituted radical in the konjak gum of described replacement is C
1~ C
10hydroxyalkyl, be preferably C
1~ C
6hydroxyalkyl; And the substitution value of described substituted radical is 0.1-0.55, be preferably 0.2-0.4.
11. methods according to claim 9, wherein, described etherification modified condition makes the ion etherificate substitution value of described etherification modified konjak gum be 0.01-1.5, is preferably 0.15-0.55; Described etherification modified condition optimization comprises: temperature of reaction is 40-90 DEG C, preferred 50-80 DEG C; Reaction times is 2-4h, is preferably 2.5-3.5h.
12. methods according to claim 9 or 11, wherein, carry out etherification modified process by substituted or unsubstituted konjak gum and comprise: be dissolved in solvent by substituted or unsubstituted konjak gum, then add alkali and etherifying agent wherein, and temperature reaction.
13. methods according to claim 12, wherein, the weight ratio of the consumption of described substituted or unsubstituted konjak gum, solvent, alkali and etherifying agent is 100:(500 ~ 700): (2 ~ 40): (1 ~ 60), are preferably 100:(550 ~ 650): (5 ~ 15): (12 ~ 40).
14. methods according to claim 12, wherein, described method also comprises: after reaction terminates, and neutralizes the mixture obtained after reaction with acid.
15. 1 kinds of water-base gel fracturing fluids, the etherification modified konjak gum that this fracturing liquid contains the etherification modified konjak gum in claim 1-8 described in any one or prepared by the method in claim 9-14 described in any one.
The application in oil production of 16. aqueous fracturing fluids according to claim 15.
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| CN107522791A (en) * | 2016-06-20 | 2017-12-29 | 中国石油化工股份有限公司 | One kind is containing sulfonic natural plant gum and preparation method and application |
| CN111944509A (en) * | 2020-08-26 | 2020-11-17 | 肯特催化材料股份有限公司 | Anti-swelling agent for shale gas fracturing |
| CN115340859A (en) * | 2022-09-23 | 2022-11-15 | 河北鑫合生物化工有限公司 | Composite polysaccharide drag reducer, composite polysaccharide slickwater fracturing fluid and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105884926A (en) * | 2016-04-25 | 2016-08-24 | 中国石油集团渤海钻探工程有限公司 | Preparation method of modified hydroxypropyl guanidine gum thickener |
| CN105884926B (en) * | 2016-04-25 | 2018-05-01 | 中国石油集团渤海钻探工程有限公司 | A kind of preparation method of modified hydroxypropyl guar thickening agent |
| CN107522791A (en) * | 2016-06-20 | 2017-12-29 | 中国石油化工股份有限公司 | One kind is containing sulfonic natural plant gum and preparation method and application |
| CN107522791B (en) * | 2016-06-20 | 2020-10-23 | 中国石油化工股份有限公司 | Vegetable gum containing sulfonic group and preparation method and application thereof |
| CN106749711A (en) * | 2016-12-28 | 2017-05-31 | 安徽工程大学 | A kind of dual etherification starch, preparation method and applications |
| CN111944509A (en) * | 2020-08-26 | 2020-11-17 | 肯特催化材料股份有限公司 | Anti-swelling agent for shale gas fracturing |
| CN111944509B (en) * | 2020-08-26 | 2022-05-03 | 肯特催化材料股份有限公司 | Anti-swelling agent for shale gas fracturing |
| CN115340859A (en) * | 2022-09-23 | 2022-11-15 | 河北鑫合生物化工有限公司 | Composite polysaccharide drag reducer, composite polysaccharide slickwater fracturing fluid and application |
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