CN102816252A - Hydroxypropyl guar gum derivative manufacturing method - Google Patents
Hydroxypropyl guar gum derivative manufacturing method Download PDFInfo
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- CN102816252A CN102816252A CN201210311183XA CN201210311183A CN102816252A CN 102816252 A CN102816252 A CN 102816252A CN 201210311183X A CN201210311183X A CN 201210311183XA CN 201210311183 A CN201210311183 A CN 201210311183A CN 102816252 A CN102816252 A CN 102816252A
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Abstract
An embodiment of the invention discloses a hydroxypropyl guar gum derivative manufacturing method including: adding GG (guar gum) and potassium hydroxide solution into chlorinated-1-butyl-3-methy imidazole solution so as to obtain initial solution; heating the initial solution for a first time at the first temperature; and cooling the heated initial solution to the room temperature, adding propylene oxide to react for a second time at the second temperature so that a reaction product is obtained. According to the method in the embodiment, reaction is carried out in an ionic liquid medium to enable each component to react under the homogeneous condition, and hydroxypropyl guar gum derivatives with different MS (molar substitution) can be obtained by selecting different ionic liquids or changing the PO (propylene oxide) quantity, so that the use ratio of the guar gum or the PO is increased. Since the reaction is carried out in the ionic liquid medium and the KOH solution is added to serve as a catalyst, a whole system is low in water content, and possibility of reaction of water with the PO is greatly decreased. The hydroxypropyl guar gum derivative manufacturing method is simple and feasible, and the reaction is easy to control.
Description
Technical field
The present invention relates to be used for the of the fracturing fluid method of manufacture in petroleum industry field, especially relate to a kind of method of making the hydroxypropyl guar gum derivative.
Background technology
Pressure break as a kind of well stimulation of transforming low permeability pay more and more widely in each field use of China, of the fracturing fluid development is also more and more faster, each oil field, the whole nation all is to be suitable for the fracturing liquid that use in this oil field according to domestic existing resource research.Sesbania gum fracturing liquid, hydroxypropyl sesbania gum fracturing liquid, Walocel MT 20.000PV (CMC) the chromium gel fracturing liquid of Dagang Oilfield development, length like the Shengli Oil Field development are celebrated type methylene polyacrylamide fracturing liquid of oil field development or the like.In order to reduce the injury of fracturing fluid residue to stratum and fracture flow capacity; Several kinds low injury fracturing fluids have been developed the beginning of the nineties again in succession, like the magic pole fracturing fluid (CT9-1) of Sichuan Hu Zhou Sweet natural gas Research Institute, the fenugreek gum fracturing liquid of petroleum exploration and development research institute Langfang branch development, SC-1 type plant gum fracturing fluid of Shengli Oil Field development or the like.These of the fracturing fluid succeeding in developing to the fracturing reform of China's low permeability oil field, have all been played great promoter action.
Guar gum is the hydrophilic polysaccharide that gathers of a kind of natural nonionic, and its staple is a polygalactomannan, and its main chain is that seminose passes through β-1,4 glycosidic link and is formed by connecting, and the side chain semi-lactosi then is to be connected on the main chain through α-1,6 glycosidic link.But owing to only contain hydroxyl in the guar gum molecular structure, so its performance is single, is of limited application, and in industry, generally all can only use as thickening material, stablizer and emulsifying agent.In order to expand its range of application, people begin to attempt in the guar gum molecule, to introduce hydroxypropyl and give its new performance.Hydroxypropylguar gum after the modification is compared with virgin rubber, and performance improves a lot, and Application Areas is widened greatly.
Existing a kind of method is under base catalysis, to use the solid-liquid inhomogeneous reaction to prepare the hydroxypropyl guar gum derivative.Though this method can access the hydroxypropylguar gum verivate, this method is owing to be under heterogeneousization condition, to prepare, thereby the utilization ratio of guar gum and propylene oxide is not high, and the stability of product is bad, causes the use range of product to be restricted.
Existing another kind of method is to use phase-transfer catalyst to prepare the method for modifying of hydroxypropylguar gum.Though this method can access the hydroxypropylguar gum verivate, the adding of phase-transfer catalyst possibly make the guar gum molecular chain degrade, and viscosity reduces, and influences its use.
Summary of the invention
One of the object of the invention provides the easily method of the manufacturing hydroxypropyl guar gum derivative of control of a kind of simple, reaction.
The utilization ratio that one of the object of the invention provides a kind of guar gum and propylene oxide is high, the method for the manufacturing hydroxypropyl guar gum derivative of the good stability of the hydroxypropyl guar gum derivative of acquisition.
The disclosed technical scheme of the embodiment of the invention comprises:
A kind of method of making the hydroxypropyl guar gum derivative is characterized in that, comprising: in chlorination-1-butyl-3-Methylimidazole solution, add guar gum and potassium hydroxide solution, obtain initial soln; Said initial soln is heated the very first time under first temperature; The said initial soln that will under first temperature, heat the very first time is cooled to room temperature and adds propylene oxide, and under second temperature, reacts for second time, obtains reaction product.
Further, said method also comprises: wash said reaction product with first scavenging solution, and with the 3rd time of said reaction product after the first rotating speed eccentric cleaning; Wash said reaction product with second scavenging solution, and with the 4th time of said reaction product after the second rotating speed eccentric cleaning; The said reaction product of oven dry under the 3rd temperature.
Further, in said guar gum and the potassium hydroxide solution, the mass ratio of Pottasium Hydroxide and guar gum is 1%～10%, and the mass ratio of water and guar gum is 0.1～0.9.
Further, said first temperature is 80 degrees centigrade, and the said very first time is 2 hours.
Further, the mass ratio of said propylene oxide and said guar gum is 0.1 to 100.
Further, said second temperature is 60 degrees centigrade to 80 degrees centigrade; Said second time is 2 hours to 12 hours.
Further, said first scavenging solution is 85% aqueous acetone solution, and said first rotating speed is 4000 rev/mins, and said the 3rd time is 15 minutes.
Further, said second scavenging solution is an acetone, and said second rotating speed is 4000 rev/mins, and said the 4th time is 15 minutes, and said the 3rd temperature is 50 degrees centigrade.
Further, said chlorination-1-butyl-3-Methylimidazole solution is chlorination-1-butyl-3-Methylimidazole ionic liquid solution.
Further, ion described in the ionic liquid is glyoxaline cation, triazole positively charged ion, tetramethyleneimine positively charged ion, azoles alkane sun from, pyridylium, piperidines positively charged ion, morpholine positively charged ion, quaternary ammonium cation 、 quaternary phosphine positively charged ion, guanidine cationoid, sulfonium salt positively charged ion, Cl
-, Br
-, ZnCl
3 -, SnCl
3 -, OH
-, BF
4 -, NO
3 -, CH
3COO
-, PF
6 -, HSO
4 2-, SO
4 2, Al
2Cl
7 -, Al
3Cl
10 -, Fe
2Cl
7 -Or Cu
2Cl
3 -
In the method for the embodiment of the invention; In ion liquid medium, react; Make each component all under the homogeneous condition, react; Can obtain the hydroxypropyl guar gum derivative of different MS through the amount of selecting for use different ionic liquids perhaps to change PO, also can improve the utilization ratio of guar gum or PO through selecting different ionic liquids for use; Owing to be in ion liquid medium, to react, added KOH solution as catalyzer, water-content is less in the whole system, compares with traditional water solution heterogeneous conditions, has reduced the possibility of water and PO reaction greatly.Method in the embodiment of the invention is simple, and reaction is control easily.
Description of drawings
Fig. 1 is the schematic flow sheet of method of the manufacturing hydroxypropyl guar gum derivative of one embodiment of the invention;
Fig. 2 is the schematic flow sheet of method of the manufacturing hydroxypropyl guar gum derivative of another embodiment of the present invention.
Embodiment
As shown in Figure 1, in one embodiment of the present of invention, a kind of method of making the hydroxypropyl guar gum derivative comprises step 10, step 12 and step 14.
In step 10, in chlorination-1-butyl-3-Methylimidazole (BmimCl) solution, add guar gum (GG) and potassium hydroxide solution, obtain initial soln.In the embodiments of the invention, the amount of each component can be provided with according to practical situation flexibly in GG and the potassium hydroxide solution, and for example, among the embodiment, the mass ratio of Pottasium Hydroxide and GG can be 1%～10%, water (H
2O) mass ratio with GG can be 0.1～0.9.
In step 12, this initial soln is heated the very first time under first temperature.The concrete value of this first temperature and the very first time can be set according to practical situation flexibly.For example, among the embodiment, first temperature can be 60 degrees centigrade to 80 degrees centigrade, and the very first time can be 2 hours to 12 hours.
In step 14, the initial soln that will under first temperature, heat the very first time is cooled to room temperature and adds propylene oxide, and under second temperature, reacts for second time, obtains reaction product.At this moment, propylene oxide ring-opening reaction and receiving on the guar gum molecule under the common katalysis of chlorination-1-butyl-3-Methylimidazole solution and alkali (being Pottasium Hydroxide) generates hydroxypropyl guar gum derivative (being reaction product).At this moment, the reaction product of acquisition is a crude product.
The concrete value of this second temperature and second time can be set according to practical situation flexibly.For example, among the embodiment, second temperature can be 60 degrees centigrade to 80 degrees centigrade, and second time can be 2 hours to 12 hours.
In the embodiments of the invention, the amount of the propylene oxide of adding can be set according to the needs of practical situation flexibly.For example, among the embodiment, the propylene oxide of adding and the mass ratio of GG can be 1.5,2.5,3,12,24 or 36.Among the embodiment, the mass ratio of propylene oxide and GG can be between 0.1～100.
Through the reaction in the step 14, can generate required hydroxypropyl guar gum derivative.
In above-mentioned steps, the reaction medium of chemical reaction (being chlorination-1-butyl-3-Methylimidazole solution) is an ionic liquid, i.e. comprise ion in chlorination-1-butyl-3-Methylimidazole solution.The ion that comprises in this ionic liquid can be selected according to the needs of practical situation flexibly.The ion that comprises in the used ionic liquid in the above method is any in following:
Positively charged ion: the five-ring positively charged ion (comprising: glyoxaline cation, triazole positively charged ion, tetramethyleneimine positively charged ion; Azoles alkane positively charged ions etc.), the six-ring positively charged ion (comprising: pyridylium, piperidines positively charged ion; Morpholine positively charged ion etc.), tetrahedron positively charged ion (comprising quaternary ammonium cation ， quaternary phosphine positively charged ion etc.); Other cationoids (comprising: guanidine cationoid, sulfonium salt positively charged ion etc.), or the like.
Negatively charged ion: the monokaryon negatively charged ion (comprising: Cl
-, Br
-, ZnCl
3 -, SnCl
3 -, OH
-, BF
4 -, NO
3 -, CH
3COO
-, PF
6 -, HSO
4 2-, SO
4 2-Deng), the multinuclear negatively charged ion (comprising: Al
2Cl
7-, Al
3Cl
10 -, Fe
2Cl
7 -, Cu
2Cl
3 -Deng), or the like.
For example; Among the embodiment, this ion is glyoxaline cation, triazole positively charged ion, tetramethyleneimine positively charged ion, azoles alkane sun from, pyridylium, piperidines positively charged ion, morpholine positively charged ion, quaternary ammonium cation 、 quaternary phosphine positively charged ion, guanidine cationoid, sulfonium salt positively charged ion, Cl-, Br-, ZnCl3-, SnCl3-, OH-, BF4-, NO3-, CH3COO-, PF6-, HSO42-, SO42, Al2Cl7-, Al3Cl10-, Fe2Cl7-or Cu2Cl3-.
As shown in Figure 2, in the additional embodiments of the present invention, on the basis of the step of previous embodiment, the method for making the hydroxypropyl guar gum derivative also comprises step 16, step 18 and step 20.
In step 16, with the reaction product that obtains in the first scavenging solution washing step 14, and with this 3rd time of reaction product after the first rotating speed eccentric cleaning.
In the embodiments of the invention, this first scavenging solution can be 85% aqueous acetone solution, and this first rotating speed can be 4000 rev/mins (r/min), and the 3rd time can be 15 minutes.Certainly, first rotating speed here and the 3rd time also can be other values that is fit to, and can select flexibly based on the needs of actual conditions.For example, among the embodiment, first rotating speed can be 3000 rev/mins to 5000 rev/mins, and the 3rd time can be 5 to 20 minutes.
In the embodiments of the invention, step 16 can repeat repeatedly.
In step 18, with the reaction product after the processing of second scavenging solution washing process step 16, and with this 4th time of reaction product after the second rotating speed eccentric cleaning.
In the embodiments of the invention, this second scavenging solution can be acetone, and this second rotating speed can be 4000 rev/mins, and the 4th time can be 15 minutes.Certainly, second rotating speed here and the 4th time also can be other values that is fit to, and can select flexibly based on the needs of actual conditions.For example, among the embodiment, second rotating speed can be 3000 rev/mins to 5000 rev/mins, and the 4th time can be 5 to 20 minutes.
In step 20, the reaction product after oven dry under the 3rd temperature is handled through step 18 obtains final finished product, i.e. the hydroxypropyl guar gum derivative.
Like this, the crude reaction product that generates in the step 14 is purified and drying through the processing of step 16, step 18 and step 20 further, obtains final purified product (being the hydroxypropyl guar gum derivative).
In the embodiments of the invention, the 3rd temperature can be 50 degrees centigrade.The 3rd temperature also can be selected other any suitable value according to the needs of practical situation, and for example, among the embodiment, the 3rd temperature can be 30 degrees centigrade to 80 degrees centigrade.
Specifically describe concrete embodiment more of the present invention below.
Embodiment 1:
In BmimCl, add GG, (KOH and GG mass ratio are 1%～10% to KOH solution, H
2O and GG mass ratio 0.1～0.9), heat 2 hours down with dissolving GG at 80 ℃.Be cooled to room temperature then, add PO, PO and GG mass ratio are 1.5; Under certain temperature, react for some time, after reaction finishes, with 85% aqueous acetone solution washing reaction product; Centrifugal 15 minutes of 4000r/min so repeats repeatedly, and then uses washing with acetone; Centrifugal 15 minutes of 4000r/min, the sample that obtains is at last dried in 50 ℃ of baking ovens.With carrying out behind the sample all-hydrolytic
1H NMR characterizes to confirm the molar substitution (MS) of this sample.The MS that finally obtains this sample is 0.06.
Embodiment 2:
In BmimCl, add GG, (KOH and GG mass ratio are 1%～10% to KOH solution, H
2O and GG mass ratio 0.1～0.9), heat 2h down with dissolving GG at 80 ℃.Be cooled to room temperature then, add PO, PO and GG mass ratio are 2.5; Under certain temperature, react for some time, after reaction finishes, with 85% aqueous acetone solution washing reaction product; Centrifugal 15 minutes of 4000r/min so repeats repeatedly, and then uses washing with acetone; Centrifugal 15 minutes of 4000r/min, the sample that obtains is at last dried in 50 ℃ of baking ovens.With carrying out behind the sample all-hydrolytic
1H NMR characterizes to confirm the MS of this sample.The MS that finally obtains this sample is 0.09.
Embodiment 3:
In BmimCl, add GG, (KOH and GG mass ratio are 1%～10% to KOH solution, H
2O and GG mass ratio 0.1～0.9), heat 2h down with dissolving GG at 80 ℃.Be cooled to room temperature then, add PO, PO and GG mass ratio are 3; Under certain temperature, react for some time, after reaction finishes, with 85% aqueous acetone solution washing reaction product; Centrifugal 15 minutes of 4000r/min so repeats repeatedly, and then uses washing with acetone; Centrifugal 15 minutes of 4000r/min, the sample that obtains is at last dried in 50 ℃ of baking ovens.With carrying out behind the sample all-hydrolytic
1H NMR characterizes to confirm the MS of this sample.The MS that finally obtains this sample is 0.11.
Embodiment 4:
In BmimCl, add GG, (KOH and GG mass ratio are 1%～10% to KOH solution, H
2O and GG mass ratio 0.1～0.9), heat 2h down with dissolving GG at 80 ℃.Be cooled to room temperature then, add PO, PO and GG mass ratio are 12; Under certain temperature, react for some time, after reaction finishes, with 85% aqueous acetone solution washing reaction product; Centrifugal 15 minutes of 4000r/min so repeats repeatedly, and then uses washing with acetone; Centrifugal 15 minutes of 4000r/min, the sample that obtains is at last dried in 50 ℃ of baking ovens.With carrying out behind the sample all-hydrolytic
1H NMR characterizes to confirm the MS of this sample.The MS that finally obtains this sample is 0.20.
Embodiment 5:
In BmimCl, add GG, (KOH and GG mass ratio are 1%～10% to KOH solution, H
2O and GG mass ratio 0.1～0.9), heat 2h down with dissolving GG at 80 ℃.Be cooled to room temperature then, add PO, PO and GG mass ratio are 24; Under certain temperature, react for some time, after reaction finishes, with 85% aqueous acetone solution washing reaction product; Centrifugal 15 minutes of 4000r/min so repeats repeatedly, and then uses washing with acetone; Centrifugal 15 minutes of 4000r/min, the sample that obtains is at last dried in 50 ℃ of baking ovens.With carrying out behind the sample all-hydrolytic
1H NMR characterizes to confirm the MS of this sample.The MS that finally obtains this sample is 0.37.
Embodiment 6:
In BmimCl, add GG, (KOH and GG mass ratio are 1%～10% to KOH solution, H
2O and GG mass ratio 0.1～0.9), heat 2h down with dissolving GG at 80 ℃.Be cooled to room temperature then, add PO, PO and GG mass ratio are 36; Under certain temperature, react for some time, after reaction finishes, with 85% aqueous acetone solution washing reaction product; Centrifugal 15 minutes of 4000r/min so repeats repeatedly, and then uses washing with acetone; Centrifugal 15 minutes of 4000r/min, the sample that obtains is at last dried in 50 ℃ of baking ovens.With carrying out behind the sample all-hydrolytic
1H NMR characterizes to confirm the MS of this sample.The MS that finally obtains this sample is 0.60.
In the method for the embodiment of the invention; In ion liquid medium, react; Make each component all under the homogeneous condition, react; Can obtain the hydroxypropyl guar gum derivative of different MS through the amount of selecting for use different ionic liquids perhaps to change PO, also can improve the utilization ratio of guar gum or PO through selecting different ionic liquids for use; Owing to be in ion liquid medium, to react, added KOH solution as catalyzer, water-content is less in the whole system, compares with traditional water solution heterogeneous conditions, has reduced the possibility of water and PO reaction greatly.Method in the embodiment of the invention is simple, and reaction is control easily, and the utilization ratio of guar gum and propylene oxide is high, the good stability of the hydroxypropyl guar gum derivative of acquisition.
More than describe the present invention through concrete embodiment, but the present invention is not limited to these concrete embodiment.It will be understood by those skilled in the art that and to make various modifications to the present invention, be equal to replacement, change or the like that these conversion all should be within protection scope of the present invention as long as do not deviate from spirit of the present invention.In addition, above many places described " embodiment " representes various embodiment, can certainly be with its all or part of being combined among the embodiment.
Claims (10)
1. a method of making the hydroxypropyl guar gum derivative is characterized in that, comprising:
In chlorination-1-butyl-3-Methylimidazole solution, add guar gum and potassium hydroxide solution, obtain initial soln;
Said initial soln is heated the very first time under first temperature;
The said initial soln that will under first temperature, heat the very first time is cooled to room temperature and adds propylene oxide, and under second temperature, reacts for second time, obtains reaction product.
2. the method for claim 1 is characterized in that, said method also comprises:
Wash said reaction product with first scavenging solution, and with the 3rd time of said reaction product after the first rotating speed eccentric cleaning;
Wash said reaction product with second scavenging solution, and with the 4th time of said reaction product after the second rotating speed eccentric cleaning;
The said reaction product of oven dry under the 3rd temperature.
3. the method for claim 1, it is characterized in that: in said guar gum and the potassium hydroxide solution, the mass ratio of Pottasium Hydroxide and guar gum is 1%～10%, and the mass ratio of water and guar gum is 0.1～0.9.
4. the method for claim 1, it is characterized in that: said first temperature is 80 degrees centigrade, the said very first time is 2 hours.
5. the method for claim 1, it is characterized in that: the mass ratio of said propylene oxide and said guar gum is 0.1 to 100.
6. the method for claim 1, it is characterized in that: said second temperature is 60 degrees centigrade to 80 degrees centigrade; Said second time is 2 hours to 12 hours.
7. method as claimed in claim 2 is characterized in that: said first scavenging solution is 85% aqueous acetone solution, and said first rotating speed is 4000 rev/mins, and said the 3rd time is 15 minutes.
8. method as claimed in claim 2 is characterized in that: said second scavenging solution is an acetone, and said second rotating speed is 4000 rev/mins, and said the 4th time is 15 minutes, and said the 3rd temperature is 50 degrees centigrade.
9. the method for claim 1, it is characterized in that: said chlorination-1-butyl-3-Methylimidazole solution is chlorination-1-butyl-3-Methylimidazole ionic liquid solution.
10. method as claimed in claim 9 is characterized in that: said ion is glyoxaline cation, triazole positively charged ion, tetramethyleneimine positively charged ion, azoles alkane sun from, pyridylium, piperidines positively charged ion, morpholine positively charged ion, quaternary ammonium cation 、 quaternary phosphine positively charged ion, guanidine cationoid, sulfonium salt positively charged ion, Cl
-, Br
-, ZnCl
3 -, SnCl
3 -, OH
-, BF
4 -, NO
3 -, CH
3COO
-, PF
6 -, HSO
4 2-, 8O
4 2, Al
2Cl
7 -, Al
3Cl
10 -, Fe
2Cl
7 -Or Cu
2Cl
3 -
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Cited By (1)
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| WO2019119208A1 (en) * | 2017-12-18 | 2019-06-27 | 苏州昕能胶体技术有限公司 | Hydroxypropyl guar gum, preparation method therefor and use thereof |
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