CN106749736A - Cross-linked amphoteric xanthan gum and preparation method thereof - Google Patents
Cross-linked amphoteric xanthan gum and preparation method thereof Download PDFInfo
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- CN106749736A CN106749736A CN201611234666.9A CN201611234666A CN106749736A CN 106749736 A CN106749736 A CN 106749736A CN 201611234666 A CN201611234666 A CN 201611234666A CN 106749736 A CN106749736 A CN 106749736A
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- 229920001285 xanthan gum Polymers 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000230 xanthan gum Substances 0.000 title abstract description 18
- 229940082509 xanthan gum Drugs 0.000 title abstract description 18
- 235000010493 xanthan gum Nutrition 0.000 title abstract description 18
- 238000004132 cross linking Methods 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 125000002091 cationic group Chemical group 0.000 claims abstract description 9
- 238000006266 etherification reaction Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 10
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 9
- 239000012065 filter cake Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical group CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 6
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 238000010936 aqueous wash Methods 0.000 claims description 4
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- -1 chloro- 2- hydroxypropyl Chemical group 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- UGTZMIPZNRIWHX-UHFFFAOYSA-K sodium trimetaphosphate Chemical compound [Na+].[Na+].[Na+].[O-]P1(=O)OP([O-])(=O)OP([O-])(=O)O1 UGTZMIPZNRIWHX-UHFFFAOYSA-K 0.000 claims description 2
- BMXILUZRCXPKOI-UHFFFAOYSA-N tripropylazanium;chloride Chemical class Cl.CCCN(CCC)CCC BMXILUZRCXPKOI-UHFFFAOYSA-N 0.000 claims description 2
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 claims 1
- 239000012295 chemical reaction liquid Substances 0.000 claims 1
- 239000012530 fluid Substances 0.000 abstract description 11
- 239000002562 thickening agent Substances 0.000 abstract description 5
- 230000003113 alkalizing effect Effects 0.000 abstract description 2
- 235000019441 ethanol Nutrition 0.000 description 13
- 238000003756 stirring Methods 0.000 description 8
- 230000008719 thickening Effects 0.000 description 7
- 238000005406 washing Methods 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 5
- 230000009974 thixotropic effect Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- 238000013019 agitation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical class O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000589636 Xanthomonas campestris Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0033—Xanthan, i.e. D-glucose, D-mannose and D-glucuronic acid units, saubstituted with acetate and pyruvate, with a main chain of (beta-1,4)-D-glucose units; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
- C09K8/685—Compositions based on water or polar solvents containing organic compounds containing cross-linking agents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/90—Compositions based on water or polar solvents containing organic compounds macromolecular compounds of natural origin, e.g. polysaccharides, cellulose
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Emergency Medicine (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention provides a cross-linking type amphoteric xanthan gum and a preparation method thereof, wherein the method comprises the steps of alkalizing the xanthan gum by using alkali in a solvent, then carrying out etherification reaction on the alkalized xanthan gum by using a cationic etherifying agent, and finally carrying out cross-linking reaction on the etherified xanthan gum by using a cross-linking agent to obtain the cross-linking type amphoteric xanthan gum. Compared with xanthan gum, the viscoelastic property and the network structure of the cross-linked amphoteric xanthan gum are obviously enhanced, and when the cross-linked amphoteric xanthan gum is used for fracturing fluid, the consumption of a thickening agent can be reduced, the viscoelastic property of the fracturing fluid can be improved, and the cost is reduced.
Description
Technical field
The invention belongs to oil mining field, specifically, it is related to a kind of cross-linking type both sexes xanthans and preparation method thereof.
A kind of especially low crosslinking degree both sexes xanthans and preparation method thereof.
Background technology
Xanthans is the macromolecule polysaccharide produced through Xanthomonas campestris fermentation by carbohydrate, intermolecular to be wound double helix
Structure, is a kind of microbial polysaccharide thickening agent of the function admirable that can replace natural plant gum, is widely used in petroleum industry, is had
There is good thickening and rheological property；Xanthans is a kind of typical pseudoplastic fluid, with good water-soluble, resistance to acids and bases
And salt tolerance, and with the characteristics of viscoelastic property is high and solid-carrying performance is good, therefore can be used as non-crosslinked fracturing fluid.
Existing xanthans as thickening agent when fracturing fluid is configured, and consumption is all larger.Application No.
201310286824.5, the Chinese invention patent of Publication No. CN103361042A, the non-crosslinked fracturing fluid of xanthans, its preparation side
Method and purposes provide a kind of preparation method of the non-crosslinked xanthans fracturing fluid of 120 DEG C of heatproof, the quality that its xanthans is used
Fraction reaches 0.6%.
It is main at present that its thickening capabilities and heat resistance are improved by being modified to xanthans, reduce making for xanthans
Use concentration.Application No. 201410475166.9, the Chinese patent application of Publication No. CN104312571A, a kind of modified xanthan
Glue thickening agent and its application in fracturing fluid is prepared provide a kind of preparation method of modified xantham gum, although modified Huang
The apparent viscosity of virgin rubber increases 1 times, but the larger (xanthans of its amount of modifier：Modifying agent=10:3), it is modified relatively costly.
Therefore, a kind of modified xantham gum thickening is researched and developed, increases its modified low cost, viscoelastic property notable, and
The concentration that xanthans is used is reduced while ensureing good solid-carrying performance, so that reduces cost, is still the problem of urgent need to resolve.
The content of the invention
It is an object of the present invention to provide a kind of cross-linking type both sexes xanthans.
Another object of the present invention is to provide a kind of preparation method of cross-linking type both sexes xanthans.
It is up to above-mentioned purpose, on the one hand, the invention provides a kind of preparation method of cross-linking type both sexes xanthans, wherein,
Methods described includes in a solvent first alkalizing xanthans using alkali, then using cationic etherifying agent to the Huang after alkalization
Virgin rubber carries out etherification reaction, and finally reuse crosslinking agent carries out cross-linking reaction to the xanthans after etherificate, obtains the cross-linking type
Both sexes xanthans.
According to some specific embodiments of the invention, wherein, counted with xanthans quality as 10 parts, alkali, cationic etherifying agent
0.2-0.3 parts, 0.3-0.5 parts and 0.1-0.2 parts is respectively with the consumption of crosslinking agent.
According to some specific embodiments of the invention, wherein, the alkali is NaOH or potassium hydroxide.
According to some specific embodiments of the invention, wherein, the cationic etherifying agent is selected from the chloro- 2- hydroxypropyl trimethylammoniums of 3-
One or more of the chloro- 2- hydroxypropyls TEBA of ammonium chloride, 3- and the chloro- 2- hydroxypropyls tripropyl ammonium chlorides of 3-.
According to some specific embodiments of the invention, wherein, the crosslinking agent is epoxychloropropane or sodium trimetaphosphate.
According to some specific embodiments of the invention, wherein, the solvent is alcohol/aqueous solution.
According to some specific embodiments of the invention, wherein, the alcohol is the one kind or many in methyl alcohol, ethanol and isopropanol
The mixing solvent quality consumption planted is 2-4 times of xanthans quality.
According to some specific embodiments of the invention, wherein, the volumetric concentration of the alcohol/aqueous solution is 70%-85%.
According to some specific embodiments of the invention, wherein, the alkalization includes adding xanthans the alcohol/aqueous solution of alkali
In, 0.5-1h is stirred at room temperature.
According to some specific embodiments of the invention, wherein, the etherification reaction includes adding cationic etherifying agent instead
Answer in solution, 1-3h is reacted at 55-70 DEG C.
According to some specific embodiments of the invention, wherein, the cross-linking reaction includes for crosslinking agent adding reaction solution
In, react 1-3h at 50-70 DEG C.
According to some specific embodiments of the invention, wherein, the reaction also includes after the completion of cross-linking reaction will reaction
Solution is cooled to room temperature, filtering, and the complete reactant of unreacted is washed away with ethanol aqueous wash, and then drying obtains the crosslinking
Type both sexes xanthans.
According to some specific embodiments of the invention, wherein, the drying is to dry 10-15h at 50-60 DEG C.
According to some specific embodiments of the invention, wherein, the ethanol aqueous wash washs away complete anti-of unreacted
After the step of answering thing is included reacting liquid filtering, filter cake is mixed equal with the ethanol water and filter cake of mass concentration 60-70%
Filtering after even, is then successively repeated the above steps with 70-80%, 80-90%, 100% ethanol water again, is finally filtered.
" repeating the above steps " described here refers to the filter cake that will be obtained after filtering again with the ethanol water of 70-80%
Filtered after well mixed, then by filter cake it is well mixed with the ethanol water of 80-90% again after filter, filter cake is again with 100%
Ethanol water (absolute ethyl alcohol) it is well mixed after filter.
Priority of the invention is using 60-70%, 70-80%, 80-90% and 100% ethanol water to filtering every time
To filter cake carry out mixing, washing, the raw material complete to wash unreacted off, wherein washing ethanol water concentration used is upper every time
Sequential selection in the range of stating, can for example be respectively 70%, 70%, 80% and 100%, or 65%, 75%, 85%,
100% etc.；And according to some specific embodiments of the invention, concentration and previous concentration difference after once are 3-
20%.
According to some specific embodiments of the invention, wherein, it is described to be filtered into suction filtration.
According to some specific embodiments of the invention, wherein, methods described is specifically included：
(1) 100 parts of mixed solvents of water/alcohol are configured；
(2) in the water in step (1)/alcohol mixed solvent, 0.2~0.3 part of alkali is added, stirring at room temperature is extremely dissolved；
(3) 10~20 parts of xanthans are added to the system in step (2), it is uniform that stirring makes it suspend, at ambient temperature
Alkalization 0.5~1 hour；
(4) under agitation, 0.3-0.5 parts of cation etherifying reagent is added to system obtained in step (3), at 55~70 DEG C
At a temperature of, react 1~3 hour；
(5) under agitation, 0.1~0.2 part of crosslinking agent is added to system obtained in step (4), in 50~70 DEG C of temperature
Under, reacting 1~3 hour, the crosslinking agent is epoxychloropropane；
(6) system obtained in step (5) is cooled to room temperature, is respectively that 60%, 80%, 90% ethanol is molten with mass concentration
Liquid and absolute ethanol washing are filtered 4 times, are dried at 60 DEG C more than 10 hours, then can obtain modified xantham gum after crushed,
That is cross-linking type both sexes xanthans.
On the other hand, present invention also offers the cross-linking type both sexes xanthans that described preparation method is prepared.
In sum, the invention provides a kind of cross-linking type both sexes xanthans and preparation method thereof.Xanthans of the invention
Have the following advantages that：
1. the preparation process of cross-linking type both sexes xanthans is simple, and raw material is easy to get, and amount of modifier is few, and be modified low cost.
2. cross-linking type both sexes xanthans has degradability, environmentally safe, is a kind of environment-friendly materials.
3., compared to xanthans, the viscoelastic property and network structure of cross-linking type both sexes xanthans been significantly enhanced, and are used for
During fracturing fluid, thickening agent consumption can be both reduced, the viscoelastic property of fracturing fluid can be improved again, so that reduces cost.
Brief description of the drawings
Fig. 1 is the apparent viscosity contrast of rear xanthan gum solution before modified.
Fig. 2 is the viscoelastic property of rear xanthan gum solution before modified.
Fig. 3 is the thixotropic property of rear xanthan gum solution before modified.
Fig. 4 is the temperature and shearing sustainability of modified xantham gum solution.
Specific embodiment
Implementation process of the invention and the beneficial effect for producing are described in detail below by way of specific embodiment, it is intended to which help is read
Reader more fully understands essence of the invention and feature, not as to this case can practical range restriction.
Embodiment 1
Prepare modified xantham gum：Under the conditions of being stirred at room temperature, in 100 parts of isopropanol-waters, (mass ratio is 8:2) mixed solvent
In, 0.25 part of NaOH is added, stir, 10 parts of xanthan rubber powders are added, it is uniform that stirring makes it suspend, in 20 DEG C of temperature
Under degree, alkalize 1 hour；Being subsequently adding 0.5 part of 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride carries out etherification reaction, in 55 DEG C of temperature
Under degree, react 2 hours；Adding 0.15 part of epoxychloropropane carries out cross-linking reaction, at a temperature of 70 DEG C, reacts 1 hour；Most
System is cooled to room temperature afterwards, is respectively that 60%, 80%, 90% ethanol solution and absolute ethanol washing filter 4 with mass concentration
It is secondary, more than 12h is dried at 60 DEG C, can obtain cross-linking type both sexes xanthans, i.e. modified xantham gum thickening after crushing.
Embodiment 2
Prepare modified xantham gum：Under the conditions of being stirred at room temperature, in 100 parts of isopropanol-waters, (mass ratio is 8:2) mixed solvent
In, 0.2 part of NaOH is added, stir, 10 parts of xanthan rubber powders are added, it is uniform that stirring makes it suspend, in 20 DEG C of temperature
Under degree, alkalize 0.5 hour；Being subsequently adding 0.3 part of chloro- 2- hydroxypropyls TEBA of 3- carries out etherification reaction, at 70 DEG C
At a temperature of, react 1 hour；Adding 0.17 part of epoxychloropropane carries out cross-linking reaction, at a temperature of 50 DEG C, reacts 3 hours；
System is finally cooled to room temperature, is respectively that 60%, 80%, 90% ethanol solution and absolute ethanol washing are filtered with mass concentration
4 times, more than 12h is dried at 60 DEG C, cross-linking type both sexes xanthans, i.e. modified xantham gum thickening are can obtain after crushing.
Embodiment 3
Prepare modified xantham gum：Under the conditions of being stirred at room temperature, in 100 parts of alcohol-waters, (mass ratio is 8:2) mixed solvent
In, 0.3 part of NaOH is added, stir, 10 parts of xanthan rubber powders are added, it is uniform that stirring makes it suspend, in 20 DEG C of temperature
Under degree, alkalize 1 hour；Being subsequently adding 0.4 part of chloro- 2- hydroxypropyls TEBA of 3- carries out etherification reaction, in 60 DEG C of temperature
Under degree, react 3 hours；Adding 0.2 part of epoxychloropropane carries out cross-linking reaction, at a temperature of 60 DEG C, reacts 2 hours；Most
System is cooled to room temperature afterwards, is respectively that 60%, 80%, 90% ethanol solution and absolute ethanol washing filter 4 with mass concentration
It is secondary, more than 12h is dried at 60 DEG C, can obtain cross-linking type both sexes xanthans, i.e. modified xantham gum thickening after crushing.
Test example 1
This test example is used to detecting 0.4% modified xantham gum thickening that embodiment of the present invention 1-3 prepares water-soluble
Apparent viscosity (170s in liquid-1), test equipment uses RheolabQC rheometers, and result of the test is shown in Table 1.
Table 1
| Detection project | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Apparent viscosity (25 DEG C)/mPas | 128.66 | 126.55 | 140.23 |
Test example 2
This test example is used to contrast the performance of the modified xantham gum in xanthan rubber powder and embodiment 1.
The apparent viscosity of xanthans after contrast before modified, in 30 DEG C, 170s-1Under, using RheolabQC rheometer measurements not
The apparent viscosity of same concentration (0.3%-0.6%) xanthan gum solution and the modified xantham gum aqueous solution, result of the test is shown in Fig. 1.Fig. 1
It is the apparent viscosity contrast of xanthan gum solution afterwards before modified, as shown in Figure 1, with modified xantham gum under concentration, (i.e. embodiment 1 is made
Standby cross-linking type both sexes xanthans) apparent viscosity be significantly greater than the apparent viscosity of xanthans, 0.6% modified xantham gum and
The apparent viscosity of 0.6% xanthans is respectively 199mPas and 85mPas, increases 134%.
The viscoelastic property of xanthans after contrast before modified, 20 DEG C, under oscillation mode, using the senior rotational rheometers of Hakke
The test systems of Mars II (rotor model C35/1 ° of TiL, diameter 35.00mm, 1 ° of cone angle), to 0.4% before modified after xanthans
The aqueous solution performs a scan (strain γ=1%, angular frequency=0.1~10rad/s), obtains viscoelasticity index G ', G ", examination
Test result and see Fig. 2.Fig. 2 is the viscoelastic property of rear xanthan gum solution before modified, as shown in Figure 2, the G ' of modified xantham gum, G "
G ', G more than xanthans ", illustrates that modified xantham gum has more preferable viscoelastic property and stronger network structure.
The thixotropic property of xanthans, at 20 DEG C, is tested using the senior rotational rheometer Mars II of Hakke after contrast before modified
System (rotor model C35/1 ° of TiL, diameter 35.00mm, 1 ° of cone angle), to 0.6% before modified after xanthan gum solution carry out
(shear rate first rises to 170s by 0 for thixotropy test-1, the time is 30s；Again by 170s-10 is down to, the time is 30s), experiment knot
Fruit sees Fig. 3.Fig. 3 is the thixotropic property of rear xanthan gum solution before modified, from the figure 3, it may be seen that the thixotropic loop area of modified xantham gum
More than the thixotropic loop area of xanthans, illustrate that the network structure of modified xantham gum formation is better than the network structure of xanthans.
Test example 3
This tests the temperature and shearing sustainability for detecting the modified xantham gum prepared in embodiment 1.
In the 2%KCl aqueous solution of 100mL, add 0.4g modified xantham gums, after it is swelling completely after tested.Experiment
Method is that measuring apparatus are with reference to oil and gas industry standard SY/T5107-2005 " aqueous fracturing fluid method of evaluating performance "
RS6000 rheometers, as a result referring to Fig. 4.
Fig. 4 is the temperature and shearing sustainability of modified xantham gum solution.As shown in Figure 4, the 0.4% of 2%KCl aqueous solution configuration
Modified xantham gum solution is in 120 DEG C, 170s-1Reservation viscosity of the condition down cut after 90 minutes still has 61mPas, and 0.4% is yellow
Virgin rubber solution is only 48mPas in 30 DEG C of apparent viscosity (see Fig. 1)；Compared with xanthan gum solution before modified, with concentration
Modified xantham gum has more preferable temperature and shearing sustainability and solid-carrying performance.
Claims (10)
1. a kind of preparation method of cross-linking type both sexes xanthans, wherein, methods described is included in a solvent first using alkali to xanthan
Glue is alkalized, and then carries out etherification reaction to the xanthans after alkalization using cationic etherifying agent, finally reuses crosslinking agent
Cross-linking reaction is carried out to the xanthans after etherificate, the cross-linking type both sexes xanthans is obtained.
2. preparation method according to claim 1, wherein, counted with xanthans quality as 10 parts, alkali, cationic etherifying agent and
The quality consumption of crosslinking agent is respectively 0.2-0.3 parts, 0.3-0.5 parts and 0.1-0.2 parts.
3. preparation method according to claim 1, wherein, the alkali is NaOH or potassium hydroxide.
4. preparation method according to claim 1, wherein, the cationic etherifying agent is selected from the chloro- 2- hydroxypropyl trimethylammoniums of 3-
One or more of the chloro- 2- hydroxypropyls TEBA of ammonium chloride, 3- and the chloro- 2- hydroxypropyls tripropyl ammonium chlorides of 3-.
5. preparation method according to claim 1, wherein, the crosslinking agent is epoxychloropropane or sodium trimetaphosphate.
6. preparation method according to claim 1, wherein, the solvent is alcohol/aqueous solution；The alcohol be preferably methyl alcohol,
One or more in ethanol and isopropanol of mixing；It is preferred that the solvent quality consumption is 4-10 times of xanthans quality；It is excellent
The volumetric concentration for selecting the alcohol/aqueous solution is 70%-85%.
7. preparation method according to claim 1, wherein, the alkalization includes adding xanthans the alcohol/aqueous solution of alkali
In, 0.5-1h is stirred at room temperature.
8. preparation method according to claim 1, wherein, the etherification reaction includes adding cationic etherifying agent and reacts
In solution, 1-3h is reacted at 55-70 DEG C；The cross-linking reaction include by crosslinking agent add reaction solution in, at 50-70 DEG C
Reaction 1-3h.
9. preparation method according to claim 1, wherein, the reaction also includes to react molten after the completion of cross-linking reaction
Liquid is cooled to room temperature, filtering, and the complete reactant of unreacted is washed away with ethanol aqueous wash, and then drying obtains the cross-linking type
Both sexes xanthans；Preferably 10-15h is dried at 50-60 DEG C；It is preferred that the ethanol aqueous wash washs away complete anti-of unreacted
After the step of answering thing is included reacting liquid filtering, filter cake is mixed equal with the ethanol water and filter cake of mass concentration 60-70%
Filtering after even, is then successively repeated the above steps with 70-80%, 80-90%, 100% ethanol water again, is finally filtered.
10. the cross-linking type both sexes xanthans that the preparation method described in claim 1~9 any one is prepared.
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| CN112110682A (en) * | 2020-08-10 | 2020-12-22 | 中交武汉港湾工程设计研究院有限公司 | High-efficiency plugging film-forming shield slurry material for emergency |
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| CN104974266A (en) * | 2014-04-10 | 2015-10-14 | 中国石油化工股份有限公司 | Etherification-modified microorganism gum and preparation method thereof, water-base gel fracturing fluid containing the microorganism gum and application thereof |
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