CN104910288B - Esterification and crosslinking derivant based on guar gum and its production and use - Google Patents
Esterification and crosslinking derivant based on guar gum and its production and use Download PDFInfo
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- CN104910288B CN104910288B CN201510324595.0A CN201510324595A CN104910288B CN 104910288 B CN104910288 B CN 104910288B CN 201510324595 A CN201510324595 A CN 201510324595A CN 104910288 B CN104910288 B CN 104910288B
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Abstract
The invention provides a kind of esterification and crosslinking derivant based on guar gum and its production and use.The present invention has, based on the esterification and crosslinking derivant of guar gum, the structure being expressed from the next：X1 O C (O) R C (O) O X2, wherein X1, X2 can be identical or different, represents guar gum molecule fragment, and R is the C of bivalence4‑C8Straight-chain aliphatic alkyl or the C of bivalence6‑C10Aromatic group.The present invention can serve as aqueous fracturing fluid thickening based on the esterification and crosslinking derivant of guar gum, and its preparation method is simple and convenient, and water-insoluble is low, and dissolution velocity is fast, can be widely used for oil-gas field fracturing.
Description
Technical field
The present invention relates to for fracturing fluid thickening agent, more particularly, to a kind of esterification and crosslinking derivant based on guar gum and its
Preparation method and purposes.
Background technology
Pressure break has been developed rapidly as the Main Yield-increasing of oil-gas reservoir, well stimulation and has extensively been applied, and fracturing fluid is pressure
Split the important component part of technology.The fracturing fluid commonly used at present is mainly the crosslinked plant gum fracturing fluid of organic metal, therein
Thickener concentration is big, water insoluble matter content is high, leads to residue content high, Low-Permeability Gas Sands is injured larger.
When melon collagen powder uses as thickening agent, water insoluble matter content is higher, and dissolving is slow.From environmental conservation with prevent ground
Layer rock seam infringement is set out, and proposes modifyed guar gum and obtains guar gum derivative, thus obtaining the more excellent thickening agent of performance, but in guar gum
In modification, reduce water insoluble matter content and keep there is contradiction between viscosity, the water-insoluble of usual guar gum derivative substantially drops
When low, its viscosity also can reduce.
Scholar is had to attempt preparing crosslinked guar gum or derivatives thereof using epoxychloropropane for cross-linking agent, though obtaining larger friendship
Connection degree, but obtained crosslinked guar gum dissolubility in water less, is not suitable for fracturing fluid field (Tang Hongbo, Wang Xiguang, Li Yan
Flat. crosslinked guar gum preparation technology [J]. Food Science, 2012,16：014；Chen Nali, Feng Huixia, Zhao Xia, etc. crosslinked carboxylic first
The preparation [J] of base guar gum. food industry science and technology, 2011,10：078.).And beet alkali ampholytic ion guar gum derivative preparation work
Skill complexity high cost.
Therefore there are the needs based on guar gum derivative thickening agent for the improvement so as to more effectively Oil ＆ Gas Productivity can be improved,
Sufficiently achieve the purpose of oil-gas reservoir pressure break.
Content of the invention
The primary and foremost purpose of the present invention is to provide a kind of esterification and crosslinking derivant based on guar gum, and more particularly, to a kind of guar gum is double
Esterification derivative thickening agent.
It is a further object to provide the preparation method of the esterification and crosslinking derivant based on guar gum.
A further object of the present invention is the purposes for aqueous fracturing fluid thickening for the esterification and crosslinking derivant based on guar gum.
Specifically, the present invention relates to technical scheme below：
1. a kind of esterification and crosslinking derivant based on guar gum, it has the structure being expressed from the next：
X1-O-C(O)-R-C(O)-O-X2
Wherein X1, X2 can be identical or different, represent guar gum molecule fragment, and R is the C of bivalence4-C8Straight-chain aliphatic alkyl
Or the C of bivalence6-C10Aromatic group, the C of described bivalence4-C8Straight-chain aliphatic alkyl or the C of bivalence6-C10Aromatic group is appointed
Choosing is selected from C1-C6Alkyl, C6-C10Aryl, C1-C6Alkoxyl, C6-C10Aryloxy group, the substituent group of halogen atom replaces.
2. the esterification and crosslinking derivant based on guar gum according to the 1st, it passes through guar gum and two ester type compounds
Ester exchange reaction is formed.
In the present invention ,-C (O)-R-C (O)-O- is the residue of two ester type compounds.
3. a kind of for preparation the 1st described in the esterification and crosslinking derivant based on guar gum method, including：Make guar gum former
Powder and two ester type compounds react in the presence of optional catalyst for ester exchange reaction.
4. the method according to the 3rd, wherein said two ester type compounds are C6-C10Straight-chain aliphatic dicarboxylic acids and
C8-C12The diester of at least one of aromatic dicarboxylic acid, preferably adipic acid diformazan (second) ester, decanedioic acid diformazan (second) ester, right
Phthalic acid diformazan (second) ester, M-phthalic acid diformazan (second) ester, phthalic acid diformazan (second) ester, naphthalenedicarboxylic acid diformazan (second)
One or more of ester mixture.
In the present invention, diformazan (second) ester represents dimethyl ester, diethylester or first, ethyl ester.
In addition, other substituent group can also be had on binary acid residue in two ester type compounds.Do not producing serious shadow
Ring two ester type compounds and guar gum esterification and crosslinking react in the case of it may be considered that it is sterically hindered and reactive, selection times
What substituent group, such substituent group preferably includes C1-C6Alkyl, C6-C10Aryl, C1-C6Alkoxyl, C6-C10Aryloxy group, halogen
Atom, etc.,
5. the method according to any of the above-described, wherein said catalyst for ester exchange reaction be base catalyst or sun from
Sub-exchange resin.
6. the method according to any of the above-described, wherein said base catalyst is sodium hydroxide, potassium hydroxide, carbonic acid
One or more of sodium, potassium carbonate, ethylenediamine, triethylamine.
7. the method according to any of the above-described, will be dry for former for guar gum dried bean noodles and be dissolved in organic wherein before ester exchange reaction
Solvent.
8. the method according to any of the above-described, wherein said organic solvent is DMF, DMSO, Ketohexamethylene, in methyl amylketone
The mixture of one or more.
9. the method according to any of the above-described, wherein said melon collagen powder with the mass ratio of two ester type compounds is
1：(0.01-2), preferably 1：(0.1-2), more preferably 1：(0.1-1), most preferably 1：(0.2-0.5).
10. the esterification and crosslinking derivant based on guar gum as described in the 1st is used for the purposes of aqueous fracturing fluid thickening.
For reaching above-mentioned purpose, the preparation method of the esterification guar gum derivative of the present invention can include following concrete steps：
(1) melon collagen powder is dried pretreatment at 80 degree；
(2) solvent being 1～10: 1 by mass ratio is mixed with pretreatment guar gum；Addition guar gum quality 0.01wt%～
The catalyst of 2wt%；
(3) stir and be warming up to 40～80 DEG C；
(4) two ester type compounds of Deca guar gum quality 1%～200%；And by-product be removed under reduced pressure, pressure -0.1～-
0.01MPa；
(5) 40～80 DEG C of decompression states are kept to react 1～10 hour；
(6) filter after reaction terminates, washing, dry, pulverize and obtain final product esterification guar gum derivative.
The present invention passes through the hydroxyl reaction in the ester group and guar gum of cross-linking agent, so that two or more guar gum molecules is handed over
It is linked togather formation space net structure (although illustrate only two guar gum molecules in structural formula to pass through cross-linking agents one
Rise, but due to there being multiple crosslinkable groups on guar gum molecule, the therefore guar gum molecule after crosslinking forms relative complex space
Network structure, for simplicity only giving two guar gum molecules and pass through cross-linking agents together simple in description
Structure), though therefore guar gum strand can be interrupted under basic or acidic conditions, the viscosity of gained crosslinking guar gum is compared with guar gum phase
Closely.
The thickening agent of the present invention is the modified thickening agent of double esterification on the basis of guar gum, using reactant liquor alkalescence to guar gum
Water-insoluble is degraded so as to water-insoluble substantially reduces compared with guar gum, can significantly reduce the injury to stratum, reach volume increase
Purpose.
The double esterification modifyed guar gum of present invention dissolution velocity in water substantially speeds compared with melon collagen powder.
Brief description
Fig. 1 is the FTIR collection of illustrative plates of the product of embodiment 1；
Fig. 2 is the FTIR collection of illustrative plates of the raw material guar gum of embodiment 1.
Specific embodiment
Raw material information
Melon collagen powder：Manufacturer is Natural Polymer Industries (Pvt) Ltd., and specification is BHV-250.
Embodiment 1：
It is dimethyl adipate used in this example, its structural formula is：
This example preparation process is as follows：
1. melon collagen powder is dried 2 hours under 80 degree；
2. 30 grams of methyl amylketones are put in there-necked flask, under stirring, be slowly added into 30 grams of melon collagen powder (powdery)；
3. stirring is warming up to 60 degree, 1 DEG C～3 DEG C of heating rate；
4. add 1.5 grams of potassium carbonate and 10ml ethanol, alkalize 15 minutes；
5. Deca contains 20 grams of the methyl amylketone of 10.8 g of adipic acid dimethyl esters, drip speed 2～3 seconds/drip；
6. decompression stirring reaction 3 hours, pressure -0.1MPa after completion of dropping；
7., after reaction terminates, with glacial acetic acid and washing with alcohol, then dry, pulverize and obtain final product.
Embodiment 2：
It is dimethyl adipate used in this example, its structural formula is：
This example preparation process is as follows：
1. melon collagen powder is dried 2 hours under 80 degree；
2. 30 grams of methyl amylketones are put in there-necked flask, under stirring, be slowly added into 30 grams of melon collagen powder (powdery)；
3. stirring is warming up to 60 degree, 1 DEG C～3 DEG C of heating rate；
4. add 1.5 grams of potassium carbonate and 10ml ethanol, alkalize 15 minutes；
5. Deca contains 20 grams of the methyl amylketone of 12.5 g of adipic acid dimethyl esters, drip speed 2～3 seconds/drip；
6. decompression stirring reaction 3 hours, pressure -0.1MPa after completion of dropping；
7., after reaction terminates, with glacial acetic acid and washing with alcohol, then dry, pulverize and obtain final product.
Embodiment 3：
It is dimethyl adipate used in this example, its structural formula is：
This example preparation process is as follows：
1. melon collagen powder is dried 2 hours under 80 degree；
2. 30 grams of methyl amylketones are put in there-necked flask, under stirring, be slowly added into 30 grams of melon collagen powder (powdery)；
3. stirring is warming up to 60 degree, 1 DEG C～3 DEG C of heating rate；
4. add 0.1 gram15 ion-exchange resins；
5. Deca contains 20 grams of the methyl amylketone of 10.8 g of adipic acid dimethyl esters, drip speed 2～3 seconds/drip；
6. decompression stirring reaction 3 hours, pressure -0.1MPa after completion of dropping；
7., after reaction terminates, with glacial acetic acid and washing with alcohol, then dry, pulverize and both obtained.
Embodiment 4：
It is dimethyl terephthalate (DMT) used in this example, its structural formula is：
Preparation process is as follows：
1. melon collagen powder is dried 2 hours under 80 degree；
2. 30 grams of methyl amylketones are put in there-necked flask, under stirring, be slowly added into 30 grams of melon collagen powder (powdery)；
3. stirring is warming up to 60 degree, 1 DEG C～3 DEG C of heating rate；
4. add 1.5 grams of potassium carbonate and 10ml ethanol, alkalize 15 minutes；
5. Deca contains 20 grams of the methyl amylketone of 12 grams of dimethyl terephthalate (DMT)s, drip speed 2～3 seconds/drip；
6. decompression stirring reaction 3 hours, pressure -0.1MPa after completion of dropping；
7., after reaction terminates, with glacial acetic acid and washing with alcohol, then dry, pulverize and obtain final product.
Embodiment 5：
It is diethyl terephthalate used in this example, its structural formula is：
Preparation process is as follows：
1. melon collagen powder is dried 2 hours under 80 degree；
2. 30 grams of methyl amylketones are put in there-necked flask, under stirring, be slowly added into 30 grams of melon collagen powder (powdery)；
3. stirring is warming up to 60 degree, 1 DEG C～3 DEG C of heating rate；
4. add 1.5 grams of potassium carbonate and 10ml ethanol, alkalize 15 minutes；
5. Deca contains 20 grams of the methyl amylketone of 13.8 grams of diethyl terephthalates, drip speed 2～3 seconds/drip；
6. decompression stirring reaction 3 hours, pressure -0.1MPa after completion of dropping；
7., after reaction terminates, with glacial acetic acid and washing with alcohol, then dry, pulverize and obtain final product.
Embodiment 6：
It is dimethyl sebacate used in this example.
Preparation process is as follows：
1. melon collagen powder is dried 2 hours under 80 degree；
2. 30 grams of DMF are put in there-necked flask, under stirring, be slowly added into 30 grams of melon collagen powder (powdery)；
3. stirring is warming up to 60 degree, 1 DEG C～3 DEG C of heating rate；
4. add 1.5 grams of potassium carbonate and 10ml ethanol, alkalize 15 minutes；
5. Deca contains DMF20 gram of 11.5 grams of dimethyl sebacates, drip speed 2～3 seconds/drip；
6. decompression stirring reaction 3 hours, pressure -0.1MPa after completion of dropping；
7., after reaction terminates, with glacial acetic acid and washing with alcohol, then dry, pulverize and obtain final product.
FTIR analyzes
Embodiment 1 product and raw material guar gum are carried out FTIR analysis respectively.Fig. 1 is the FTIR collection of illustrative plates of product, and Fig. 2 is
The FTIR collection of illustrative plates of raw material guar gum.The 1739cm increasing in Fig. 1-1Place peak is ester group C=O characteristic peak, shows in guar gum molecular structure
Middle introducing ester group, meets the esterification and crosslinking derivant structure of X1-O-C (O)-R-C (O)-O-X2 guar gum.
Performance evaluation：
According to 2005《SY/T 5107-2005 aqueous fracturing fluid method of evaluating performance》Esterification guar gum derivative is entered
Row performance evaluation.Table 1 below is the performance indications of esterification guar gum derivative and melon collagen powder.
Table 1 is esterified the performance indications of guar gum derivative and melon collagen powder
As it can be seen from table 1 esterification guar gum is faster than melon collagen powder dissolution velocity, improve efficiency of construction；Secondly water-insoluble
Content decreases, and decreases the injury to stratum for the fracturing fluid.
In the present invention, with ester exchange reaction principle, anti-with the hydroxyl of guar gum molecule by the ester group of dibasic acid esters cross-linking agent
Should, make two or more guar gum molecule cross-links form space net structure together.Crosslinking after ester exchange reaction
Guar gum, its dissolving speed substantially speeds, and water-insoluble substantially reduces.
These are only the preferred embodiments of the present invention, and non-limiting invention protection domain, all spirit in the present invention
It is all contained in protection scope of the present invention with any modification, replacement or the improvement within principle etc..
Claims (8)
1. a kind of method of the esterification and crosslinking derivant for preparation based on guar gum, the described esterification and crosslinking derivant based on guar gum
There is the structure being expressed from the next：
X1-O-C(O)-R-C(O)-O-X2
Wherein X1, X2 can be identical or different, represent guar gum molecule fragment, and R is the C of bivalence4-C8Straight-chain aliphatic alkyl or two
The C of valency6-C10Aromatic group, the C of described bivalence4-C8Straight-chain aliphatic alkyl or the C of bivalence6-C10Aromatic group optionally quilt
Selected from C1-C6Alkyl, C6-C10Aryl, C1-C6Alkoxyl, C6-C10Aryloxy group, the substituent group of halogen atom replaces,
Methods described includes：Make melon collagen powder and two ester type compounds anti-in the presence of optional catalyst for ester exchange reaction
Should.
2. method according to claim 1, wherein said two ester type compounds are C6-C10Straight-chain aliphatic dicarboxylic acids and C8-
C12The diester of at least one of aromatic dicarboxylic acid.
3. method according to claim 2, wherein said two ester type compounds are adipic acid diformazan (second) ester, decanedioic acid two
First (second) ester, p-phthalic acid diformazan (second) ester, M-phthalic acid diformazan (second) ester, phthalic acid diformazan (second) ester, naphthalene two
One or more of formic acid diformazan (second) ester mixture.
4. method according to claim 1, wherein said catalyst for ester exchange reaction is base catalyst or cation is handed over
Change resin.
5. method according to claim 4, wherein said base catalyst is sodium hydroxide, potassium hydroxide, sodium carbonate, carbon
One or more of sour potassium, ethylenediamine, triethylamine.
6. method according to claim 1, will be dry for former for guar gum dried bean noodles and be dissolved in organic solvent wherein before ester exchange reaction.
7. method according to claim 6, wherein said organic solvent is DMF, DMSO, Ketohexamethylene, in methyl amylketone one
Plant or several mixture.
8. method according to claim 1, the mass ratio of wherein said melon collagen powder and two ester type compounds is 1：
(0.01-2).
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1791616A (en) * | 2003-05-21 | 2006-06-21 | 西巴特殊化学品控股有限公司 | A process for the preparation of hydroxy polymer esters and their use |
| CN102498131A (en) * | 2009-09-10 | 2012-06-13 | 卡吉尔公司 | Microprocessing in heterogeneous reaction mixtures |
| CN102827300A (en) * | 2012-08-30 | 2012-12-19 | 华南理工大学 | Preparation method and application of hydrophobic modified guar gum |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1791616A (en) * | 2003-05-21 | 2006-06-21 | 西巴特殊化学品控股有限公司 | A process for the preparation of hydroxy polymer esters and their use |
| CN102498131A (en) * | 2009-09-10 | 2012-06-13 | 卡吉尔公司 | Microprocessing in heterogeneous reaction mixtures |
| CN102827300A (en) * | 2012-08-30 | 2012-12-19 | 华南理工大学 | Preparation method and application of hydrophobic modified guar gum |
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