CN104910288A - Esterification crosslinking derivative based on guar gum as well as preparation method and use thereof - Google Patents
Esterification crosslinking derivative based on guar gum as well as preparation method and use thereof Download PDFInfo
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- CN104910288A CN104910288A CN201510324595.0A CN201510324595A CN104910288A CN 104910288 A CN104910288 A CN 104910288A CN 201510324595 A CN201510324595 A CN 201510324595A CN 104910288 A CN104910288 A CN 104910288A
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- melon
- ester
- esterification
- guar gum
- glue
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Abstract
The invention provides an esterification crosslinking derivative based on guar gum as well as a preparation method and use thereof. The esterification crosslinking derivative based on guar gum is provided with the structure represented by the following formula: X1-O-C(O)-R-C(O)-O-X2, wherein the X1 and the X2 can be the same or different to represent molecular fragments of the guar gum, and R is a divalent C4-C8 linear chain aliphatic alkyl or divalent C6-C10 aromatic group. The esterification crosslinking derivative based on the guar gum provided by the invention can be used for thickening a water-based fracturing fluid; and the preparation method is simple and convenient, the water insoluble is low, the dissolving speed is fast, and the derivative can be widely used for the fracturing of an oil-gas field.
Description
Technical field
The present invention relates to for of the fracturing fluid viscosifying agent, particularly relate to a kind of esterification and crosslinking derivative based on melon glue and its production and use.
Background technology
Pressure break has been developed rapidly and widespread use as the Main Yield-increasing of hydrocarbon-bearing pool, well stimulation, and fracturing liquid is the important component part of fracturing technique.Fracturing liquid conventional is at present mainly the crosslinked plant gum fracturing fluid of organo-metallic, and thickener concentration is wherein large, water insoluble matter content is high, causes residue content high, larger to Low-Permeability Gas Sands injury.
When melon collagen powder uses as thickening material, water insoluble matter content is higher, dissolves slowly.From environment protection and prevent formation rock stitch infringement; propose modifyed guar gum and obtain guar gum derivative; thus obtain the more excellent thickening material of performance; but in the modification of melon glue; reduce water insoluble matter content and keep there is contradiction between viscosity; when the water-insoluble of usual guar gum derivative obviously reduces, its viscosity also can reduce.
Scholar is had to attempt using epoxy chloropropane for the crosslinked melon glue or derivatives thereof of linking agent preparation, though obtain larger degree of crosslinking, but obtained crosslinked melon glue solubleness in water is little, be not suitable for fracturing liquid field (Tang Hongbo, Wang Xiguang, Li Yanping. crosslinked guar gum preparation technology [J]. Food science, 2012,16:014; Chen Nali, Feng Huixia, Zhao Xia, etc. the preparation [J] of crosslinked carboxymethylguar. foodstuffs industry science and technology, 2011,10:078.).And beet alkali ampholytic ion guar gum derivative complicated process of preparation cost is high.
Therefore exist and improve based on the needs of guar gum derivative thickening material, can more effective raising Oil & Gas Productivity, fully reach the object of hydrocarbon-bearing pool pressure break.
Summary of the invention
Primary and foremost purpose of the present invention is to provide a kind of esterification and crosslinking derivative based on melon glue, particularly relates to a kind of melon glue double esterification derivative thickening material.
Another object of the present invention is to provide the preparation method of the esterification and crosslinking derivative based on melon glue.
Another object of the present invention is for the purposes of aqueous fracturing fluid thickening based on the esterification and crosslinking derivative of melon glue.
Specifically, the present invention relates to following technical scheme:
1., based on an esterification and crosslinking derivative for melon glue, it has the structure be expressed from the next:
X1-O-C(O)-R-C(O)-O-X2
Wherein X1, X2 can be identical or different, and represent melon xanthan molecule fragment, R is the C of divalence
4-C
8the C of straight-chain aliphatic alkyl or divalence
6-C
10aromatic group, the C of described divalence
4-C
8the C of straight-chain aliphatic alkyl or divalence
6-C
10aromatic group is optionally selected from C
1-C
6alkyl, C
6-C
10aryl, C
1-C
6alkoxyl group, C
6-C
10aryloxy, the substituting group of halogen atom replaces.
2. the esterification and crosslinking derivative based on melon glue according to the 1st, it is formed by the transesterification reaction of melon glue and two ester compounds.
In the present invention ,-C (O)-R-C (O)-O-is the residue of two ester compounds.
3. for the preparation of a method for the esterification and crosslinking derivative based on melon glue described in the 1st, comprising: react under making the existence of the catalyst for ester exchange reaction of melon collagen powder and the choosing in office of two ester compounds.
4. the method according to the 3rd, wherein said two ester compounds are C
6-C
10straight-chain aliphatic dicarboxylic acid and C
8-C
12the diester of at least one in aromatic dicarboxylic acid, is preferably one or more mixtures in hexanodioic acid diformazan (second) ester, sebacic acid diformazan (second) ester, terephthalic acid diformazan (second) ester, m-phthalic acid diformazan (second) ester, phthalic acid diformazan (second) ester, naphthalic acid diformazan (second) ester.
In the present invention, diformazan (second) ester represents dimethyl ester, diethyl ester or first, ethyl ester.
In addition, in two ester compounds, diprotic acid residue can also have other substituting group.When not producing the esterification and crosslinking having a strong impact on two ester compounds and melon glue and reacting, can consider that it is sterically hindered and reactive, select any substituting group, such substituting group preferably includes C
1-C
6alkyl, C
6-C
10aryl, C
1-C
6alkoxyl group, C
6-C
10aryloxy, halogen atom, etc.,
5. the method according to above-mentioned any one, wherein said catalyst for ester exchange reaction is basic catalyst or Zeo-karb.
6. the method according to above-mentioned any one, wherein said basic catalyst is one or more in sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, quadrol, triethylamine.
7. the method according to above-mentioned any one, wherein before transesterification reaction by dry for melon collagen dried bean noodles and be dissolved in organic solvent.
8. the method according to above-mentioned any one, wherein said organic solvent is the mixture of one or more in DMF, DMSO, pimelinketone, methyl amylketone.
9. the method according to above-mentioned any one, the mass ratio of wherein said melon collagen powder and two ester compounds is 1:(0.01-2), preferred 1:(0.1-2), more preferably 1:(0.1-1), most preferably 1:(0.2-0.5).
10. the esterification and crosslinking derivative based on melon glue as described in the 1st is used for the purposes of aqueous fracturing fluid thickening.
For achieving the above object, the preparation method of esterification guar gum derivative of the present invention can comprise following concrete steps:
(1) melon collagen powder is dried pre-treatment at 80 degree;
(2) by mass ratio be 1 ~ 10: 1 solvent mix with pre-treatment melon glue; Add the catalyzer of melon colloid amount 0.01wt% ~ 2wt%;
(3) stir and be warming up to 40 ~ 80 DEG C;
(4) two ester compounds of melon colloid amount 1% ~ 200% are dripped; And decompression removing by product, pressure-0.1 ~-0.01MPa;
(5) 40 ~ 80 DEG C of decompression state reactions 1 ~ 10 hour are kept;
(6) reaction terminates rear filtration, and washing, dry, pulverize and obtain esterification guar gum derivative.
The present invention is by the hydroxyl reaction in the ester group of linking agent and melon glue, make two or more melon xanthan molecule formation space net structure crosslinked together (although illustrate only two melon xanthan molecules in structural formula by cross-linking agents together, but due to melon xanthan molecule having multiple crosslinkable groups, therefore the melon xanthan molecule after being cross-linked forms the space net structure of relative complex, in order to for simplicity in specification sheets, only give two melon xanthan molecules by cross-linking agents simple structure together), though therefore melon xanthan molecule chain can be interrupted under basic or acidic conditions, but the viscosity that gained is cross-linked melon glue is close compared with melon glue.
Thickening material of the present invention is the thickening material of double esterification modification on melon matrix plinth, utilizes the alkalescence of reaction solution to degrade to melon glue insolubles, make its water-insoluble comparatively melon glue obviously reduce, significantly can reduce the injury of formation, reach the object of volume increase.
Double esterification modifyed guar gum of the present invention in water dissolution rate comparatively melon collagen powder obviously speed.
Accompanying drawing explanation
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 melon glue of embodiment 1.
Embodiment
Raw material information
Melon collagen powder: manufacturer is Natural Polymer Industries (Pvt) Ltd., and specification is BHV-250.
Embodiment 1:
Use dimethyl adipate 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 into there-necked flask, under stirring, slowly add 30 grams of melon collagen powder (powdery);
3. stir and be warming up to 60 degree, temperature rise rate 1 DEG C ~ 3 DEG C;
4. add salt of wormwood and the 10ml ethanol of 1.5 grams, alkalize 15 minutes;
5. drip the methyl amylketone 20 grams containing 10.8 g of adipic acid dimethyl esters, drip speed 2 ~ 3 seconds/drip;
6. dropwise rear decompression stirring reaction 3 hours, pressure-0.1MPa;
7., after reaction terminates, by Glacial acetic acid and washing with alcohol, then dry, pulverize and get final product.
Embodiment 2:
Use dimethyl adipate 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 into there-necked flask, under stirring, slowly add 30 grams of melon collagen powder (powdery);
3. stir and be warming up to 60 degree, temperature rise rate 1 DEG C ~ 3 DEG C;
4. add salt of wormwood and the 10ml ethanol of 1.5 grams, alkalize 15 minutes;
5. drip the methyl amylketone 20 grams containing 12.5 g of adipic acid dimethyl esters, drip speed 2 ~ 3 seconds/drip;
6. dropwise rear decompression stirring reaction 3 hours, pressure-0.1MPa;
7., after reaction terminates, by Glacial acetic acid and washing with alcohol, then dry, pulverize and get final product.
Embodiment 3:
Use dimethyl adipate 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 into there-necked flask, under stirring, slowly add 30 grams of melon collagen powder (powdery);
3. stir and be warming up to 60 degree, temperature rise rate 1 DEG C ~ 3 DEG C;
4. add 0.1 gram
15 ion-exchange resins;
5. drip the methyl amylketone 20 grams containing 10.8 g of adipic acid dimethyl esters, drip speed 2 ~ 3 seconds/drip;
6. dropwise rear decompression stirring reaction 3 hours, pressure-0.1MPa;
7., after reaction terminates, by Glacial acetic acid and washing with alcohol, then dry, pulverize and both obtained.
Embodiment 4:
Use dimethyl terephthalate (DMT) 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 into there-necked flask, under stirring, slowly add 30 grams of melon collagen powder (powdery);
3. stir and be warming up to 60 degree, temperature rise rate 1 DEG C ~ 3 DEG C;
4. add salt of wormwood and the 10ml ethanol of 1.5 grams, alkalize 15 minutes;
5. drip the methyl amylketone 20 grams containing 12 grams of dimethyl terephthalate (DMT), drip speed 2 ~ 3 seconds/drip;
6. dropwise rear decompression stirring reaction 3 hours, pressure-0.1MPa;
7., after reaction terminates, by Glacial acetic acid and washing with alcohol, then dry, pulverize and get final product.
Embodiment 5:
Use diethyl terephthalate 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 into there-necked flask, under stirring, slowly add 30 grams of melon collagen powder (powdery);
3. stir and be warming up to 60 degree, temperature rise rate 1 DEG C ~ 3 DEG C;
4. add salt of wormwood and the 10ml ethanol of 1.5 grams, alkalize 15 minutes;
5. drip the methyl amylketone 20 grams containing 13.8 grams of diethyl terephthalates, drip speed 2 ~ 3 seconds/drip;
6. dropwise rear decompression stirring reaction 3 hours, pressure-0.1MPa;
7., after reaction terminates, by Glacial acetic acid and washing with alcohol, then dry, pulverize and get final product.
Embodiment 6:
Dimethyl sebacate is 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 into there-necked flask, under stirring, slowly add 30 grams of melon collagen powder (powdery);
3. stir and be warming up to 60 degree, temperature rise rate 1 DEG C ~ 3 DEG C;
4. add salt of wormwood and the 10ml ethanol of 1.5 grams, alkalize 15 minutes;
5. drip the DMF20 gram containing 11.5 grams of dimethyl sebacates, drip speed 2 ~ 3 seconds/drip;
6. dropwise rear decompression stirring reaction 3 hours, pressure-0.1MPa;
7., after reaction terminates, by Glacial acetic acid and washing with alcohol, then dry, pulverize and get final product.
FTIR analyzes
Embodiment 1 product and raw material melon glue 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 melon glue.The 1739cm increased in Fig. 1
-1peak, place is ester group C=O characteristic peak, shows to introduce ester group in melon xanthan molecule structure, meets the esterification and crosslinking derivant structure of X1-O-C (O)-R-C (O)-O-X2 melon glue.
Performance evaluation:
According to " the SY/T 5107-2005 aqueous fracturing fluid method of evaluating performance " of 2005, performance evaluation is carried out to esterification guar gum derivative.With the performance index that following table 1 is esterification guar gum derivative and melon collagen powder.
The performance index of table 1 esterification guar gum derivative and melon collagen powder
As can be seen from Table 1, esterification melon glue is faster than melon collagen powder dissolution rate, improves operating efficiency; Secondly water insoluble matter content decreases, and decreases the injury of fracturing liquid formation.
In the present invention, use transesterification reaction principle, by the ester group of dibasic acid esters linking agent and the hydroxyl reaction of melon xanthan molecule, make two or more melon xanthan molecule formation space net structure crosslinked together.Crosslinked melon glue after transesterification reaction, its dissolving speed obviously speeds, and water-insoluble obviously reduces.
These are only the preferred embodiments of the present invention, and non-limiting invention protection domain, all any amendments within the spirit and principles in the present invention, replacement or improvement etc. are all included in protection scope of the present invention.
Claims (10)
1., based on an esterification and crosslinking derivative for melon glue, it has the structure be expressed from the next:
X1-O-C(O)-R-C(O)-O-X2
Wherein X1, X2 can be identical or different, and represent melon xanthan molecule fragment, R is the C of divalence
4-C
8the C of straight-chain aliphatic alkyl or divalence
6-C
10aromatic group, the C of described divalence
4-C
8the C of straight-chain aliphatic alkyl or divalence
6-C
10aromatic group is optionally selected from C
1-C
6alkyl, C
6-C
10aryl, C
1-C
6alkoxyl group, C
6-C
10aryloxy, the substituting group of halogen atom replaces.
2. the esterification and crosslinking derivative based on melon glue according to claim 1, it is formed by the transesterification reaction of melon glue and two ester compounds.
3. for the preparation of a method for the esterification and crosslinking derivative based on melon glue according to claim 1, comprising: react under making the existence of the catalyst for ester exchange reaction of melon collagen powder and the choosing in office of two ester compounds.
4. method according to claim 3, wherein said two ester compounds are C
6-C
10straight-chain aliphatic dicarboxylic acid and C
8-C
12the diester of at least one in aromatic dicarboxylic acid, is preferably one or more mixtures in hexanodioic acid diformazan (second) ester, sebacic acid diformazan (second) ester, terephthalic acid diformazan (second) ester, m-phthalic acid diformazan (second) ester, phthalic acid diformazan (second) ester, naphthalic acid diformazan (second) ester.
5. method according to claim 3, wherein said catalyst for ester exchange reaction is basic catalyst or Zeo-karb.
6. method according to claim 5, wherein said basic catalyst is one or more in sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, quadrol, triethylamine.
7. method according to claim 3, wherein before transesterification reaction by dry for melon collagen dried bean noodles and be dissolved in organic solvent.
8. method according to claim 7, wherein said organic solvent is the mixture of one or more in DMF, DMSO, pimelinketone, methyl amylketone.
9. method according to claim 3, the mass ratio of wherein said melon collagen powder and two ester compounds is 1: (0.01-2).
10. the esterification and crosslinking derivative based on melon glue as claimed in claim 1 is used for the purposes of aqueous fracturing fluid thickening.
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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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Granted publication date: 20170301 Termination date: 20190612 |