CN108641010A - A kind of preparation method of modified welan gum - Google Patents
A kind of preparation method of modified welan gum Download PDFInfo
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- CN108641010A CN108641010A CN201810660307.2A CN201810660307A CN108641010A CN 108641010 A CN108641010 A CN 108641010A CN 201810660307 A CN201810660307 A CN 201810660307A CN 108641010 A CN108641010 A CN 108641010A
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- welan gum
- method described
- citrate
- reaction
- phase transfer
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- 229920002310 Welan gum Polymers 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims abstract description 20
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 230000004048 modification Effects 0.000 claims abstract description 10
- 238000012986 modification Methods 0.000 claims abstract description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 239000011780 sodium chloride Substances 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 5
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 5
- 239000001103 potassium chloride Substances 0.000 claims description 5
- 235000011164 potassium chloride Nutrition 0.000 claims description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000020477 pH reduction Effects 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- AJSHDAOMUKXVDC-UHFFFAOYSA-N butan-1-amine;sulfuric acid Chemical compound CCCC[NH3+].OS([O-])(=O)=O AJSHDAOMUKXVDC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 2
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 2
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- VBQDSLGFSUGBBE-UHFFFAOYSA-N benzyl(triethyl)azanium Chemical group CC[N+](CC)(CC)CC1=CC=CC=C1 VBQDSLGFSUGBBE-UHFFFAOYSA-N 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 125000003963 dichloro group Chemical group Cl* 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 20
- 239000000243 solution Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 125000005909 ethyl alcohol group Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- HWPKGOGLCKPRLZ-UHFFFAOYSA-M monosodium citrate Chemical compound [Na+].OC(=O)CC(O)(C([O-])=O)CC(O)=O HWPKGOGLCKPRLZ-UHFFFAOYSA-M 0.000 description 3
- 239000002524 monosodium citrate Substances 0.000 description 3
- 235000018342 monosodium citrate Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920002907 Guar gum Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical group [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 150000004816 dichlorobenzenes Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 239000000665 guar gum Substances 0.000 description 2
- 229960002154 guar gum Drugs 0.000 description 2
- 235000010417 guar gum Nutrition 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 239000003129 oil well Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- LRZSAGKIMYFLHY-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;dihydrate Chemical class O.O.OC(=O)CC(O)(C(O)=O)CC(O)=O LRZSAGKIMYFLHY-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 229940099112 cornstarch Drugs 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 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
- 230000006872 improvement Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- 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
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses a kind of preparation methods of modified welan gum, including welan gum is reacted with citrate in the presence of acidulant, phase transfer catalyst and reaction dissolvent, obtain modified welan gum.The modification welan gum that the method for the present invention is prepared, increases cross-linking properties, solves the problems, such as that welan gum is water-soluble bad, while its viscosity is remarkably reinforced, viscosity increases compared to unmodified welan gum viscosity.
Description
Technical field
The present invention relates to a kind of method of modifying of microbial polysaccharide, more particularly to a kind of preparation method of modified welan gum.
Background technology
Oil is a kind of non-renewable energy resources, and China is very huge to the demand of oil.But the oil field of China is basic
All enter the middle and later periods of exploitation, moisture content rises, reservoir permeability decline have become oil exploitation faced it is main
Problem.It is common improvement oil well permeability to take pressure break seam to oil well, improves oil recovery efficiency, increases the means of yield.And
Water-based fracturing is that one of which technology is the most ripe, the maximum pressing crack construction method of cost advantage.Traditional fracturing fluid is with guar gum
As thickener, slow with liquid speed degree, construction efficiency is low.
Welan gum is a kind of macromolecule polysaccharide polymer, generally using cornstarch as raw material, is undergone microbial fermentation obtained.
The molecular structure of welan gum is similar with guar gum, has preferable thickening property, thermal stability, ph stability, salt tolerance etc..But
That its own viscosity is not high, water-soluble relatively low, solution rate is slow, be affect its as fracturing fluid thickener use it is important because
Element.
Invention content
Goal of the invention：In order to solve the technical problems existing in the prior art, the present invention provides a kind of modified welan gums
Preparation method.
It is a further object to provide the modification welan gums that the preparation method of the modified welan gum is prepared.
Technical solution：The preparation method of modified welan gum of the present invention, including welan gum and citrate are being acidified
It is reacted in the presence of agent, phase transfer catalyst and reaction dissolvent, obtains modified welan gum.
The citrate is the sodium salt or sylvite of citric acid, preferably sodium dihydrogen citrate or citrate dihydrate trisodium.
Welan gum and the molar ratio of citrate are 6: 7~3: 28, preferably 1: (1.2~3.5), more preferably 1: (1.5~2.5).
The acidulant is hydrochloric acid, a concentration of 1~6mol/L, preferably 1mol/L.
The phase transfer catalyst is quaternary ammonium salt-type phase transfer catalyst, and quaternary ammonium salt-type phase transfer catalyst is preferably benzyl
Triethylammonium chloride, etamon chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, trioctylphosphine first
One in ammonium chloride, dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, trimethyloctadecyl ammonium chloride
Kind is several, wherein the suspended best results of trimethyloctadecyl ammonium chloride.The mass ratio of welan gum and phase transfer catalyst is
(1~2): 1, preferably 1: 1.
The reaction dissolvent is one or more of aromatic hydrocarbon, the aromatic hydrocarbon of halogen substitution, water.
Preferably, reaction dissolvent is benzene,toluene,xylene, chlorobenzene, dichloro-benzenes, one or more of water, more preferably
Toluene and water.
Reaction temperature is 80~120 DEG C, preferably 80 DEG C.Reaction time be 6~12h, preferably 6~8h, more preferably
6h。
Reaction carries out under agitation, and speed of agitator is 450~550rpm, preferably 500~550rpm.
Reaction pressure is normal pressure.
Preferably, the preparation method of the modified welan gum, includes the following steps：
(1) saline citrate pH is first adjusted to 2~4 using acidulant, the saline citrate after being acidified；
(2) welan gum and the second reaction dissolvent are formed into suspension by phase transfer catalyst, then in the suspension
The middle saline citrate being added after the acidification that step (1) obtains, is reacted, and modified welan gum is obtained.
The saline citrate after acidification that step (1) obtains is added in the suspension in 10~60min,
Then it is modified reaction at reaction conditions again, the water solubility and viscosity of finally obtained modified welan gum can obtain
It further increases.
In step (1), saline citrate pH is first preferably adjusted to 3 using acidulant.
In step (1), a concentration of 0.02~0.07g/mL of saline citrate, preferably 0.03~0.05g/mL.
In step (2), second reaction dissolvent is benzene,toluene,xylene, chlorobenzene, one or more of dichloro-benzenes,
Preferably toluene.The mass volume ratio of the welan gum and the second reaction dissolvent is 60-70g/L, preferably 62.5g/L.Accordingly
, the first reaction dissolvent is the water in step (1).
The post-processing approach of the reaction is：Reaction solution is collected, insoluble organic of welan gum of citrate modification is poured into
So that product is precipitated in solvent, filters, drying, up to modified welan gum after crushing.
The organic solvent that the welan gum of the citrate modification is insoluble is ethyl alcohol.
Drying temperature is 50~70 DEG C, preferably 60 DEG C.Drying time is 12-30h.
The modification welan gum that the above method is prepared is also within protection scope of the present invention.
Modifying agent used in the present invention is citrate.
Fig. 1 and Fig. 2 are seen respectively with the IR spectrograms of modified welan gum before modified.Welan gum carboxylated modification be exactly
- C (CH are originally added on the basis of structure2COOH)2This structure of OH.In 3400cm-1Left and right is the stretching vibration of-OH
Peak, apparent peak is reinforced in Fig. 2, shows to increase-OH；Modified welan gum is in 2400cm-1Left and right occurs, on corresponding citric acid
Carboxyl asymmetric stretch, the molecular structure of surface citric acid adds in modified product；In 1600cm-1Left and right is C=O's
The peak of stretching vibration, apparent peak is reinforced in Fig. 2, shows to increase C=O.
Advantageous effect：The modification welan gum that the method for the present invention is prepared, increases cross-linking properties, solves welan gum water
The bad problem of dissolubility, while its viscosity is remarkably reinforced, viscosity increases compared to unmodified welan gum viscosity.
Description of the drawings
Fig. 1 is welan gum IR spectrograms.
Fig. 2 is the IR spectrograms of the modification welan gum of the present invention.
Specific implementation mode
In following embodiment, the detection method of viscosity is as follows：
Product 0.6g is taken, is dissolved into 100g water, the solution of 0.6wt% is made into.Water bath with thermostatic control controls temperature at 25 DEG C, uses
Viscosimeter measures its viscosity.
Embodiment 1：
2.414g citrate dihydrates trisodium (8.208mmol, 3.04eq) is dissolved in 50mL water, is adjusted with 1mol/L hydrochloric acid
PH to 3 or so, wiring solution-forming I；In three-necked flask, 5g welan gums (2.7mmo1) and 5g trimethyloctadecyl ammonium chlorides are taken
It is mixed in the toluene of 80ml under stirring conditions, is configured to the suspension of 62.5g/L, it is suspended that solution I is slowly added to this
In liquid, being stirred under the conditions of rotating speed is 450rpm makes it fully dissolve；8h is reacted under normal pressure, 80 DEG C, 450rpm stirring conditions,
Reaction solution is taken out, pouring into a large amount of absolute ethyl alcohols makes product be precipitated, and washs, and filters, and for 24 hours, modified Wei Lan is made in drying at 60 DEG C
Glue product.Product dissolves in 2wt%KCl solution 400mL, dissolving in 2h.It takes product to be configured to 0.6wt% aqueous solutions, uses
It is 0.0494pa.s. that the fast rotational viscometer of ZNN-D6 types six measures viscosity under conditions of rotating speed is 300r/min
Embodiment 2：
0.87g sodium dihydrogen citrates (4.104mmol, 1.52eq) are dissolved in 30mL water, with 1mol/L salt acid for adjusting pH to 3
Left and right, wiring solution-forming I；In three-necked flask, 5g welan gums (2.7mmol) is taken to be stirred with 5g trimethyloctadecyls ammonium chloride
Under conditions of be mixed in the toluene of 80ml, be configured to the suspension of 62.5g/L, solution I be slowly added in the suspension,
Stirring allows it fully to dissolve under the conditions of rotating speed is 450rpm；6h is reacted under normal pressure, 80 DEG C, 550rpm stirring conditions, is taken out anti-
Liquid is answered, pouring into a large amount of absolute ethyl alcohols makes product be precipitated, and washs, and filters, and for 24 hours, modified welan gum product is made in drying at 60 DEG C.
Product dissolves in 2wt%KC1 solution 400mL, dissolving in 2h.It takes product to be configured to 0.6wt% aqueous solutions, uses ZNN-D6 types
Six fast rotational viscometers measure viscosity 0.0532pa.s. under conditions of rotating speed is 300r/min
Embodiment 3：
1.39g (2.43eq) sodium dihydrogen citrate is dissolved in 30mL water, with 1mol/L salt acid for adjusting pH to 3 or so, is made into
Solution I；In three-necked flask, 5g welan gums is taken to be mixed in 80ml under stirring conditions with 5g trimethyloctadecyl ammonium chlorides
Toluene in, be configured to the suspension of 62.5g/L, solution I be slowly added in the suspension, rotating speed be 450rpm under the conditions of
Stirring allows it fully to dissolve；6h is reacted under normal pressure, 80 DEG C, 500rpm stirring conditions, takes out reaction solution, pours into a large amount of anhydrous second
So that product is precipitated in alcohol, wash, filter, for 24 hours, modified welan gum product is made in drying at 60 DEG C.Product is in 2wt%KCl solution
It is dissolved in 400mL, dissolving in 2h.It takes product to be configured to 0.6wt% aqueous solutions, is being turned using the fast rotational viscometer of ZNN-D6 types six
It is 0.0535pa.s. that speed measures viscosity under conditions of being 300r/min
Embodiment 4：
It is same as Example 1, it differs only in：
Phase transfer catalyst is benzyltriethylammoinium chloride, and the mass ratio of welan gum and phase transfer catalyst is 1.5: 1.Instead
Answer solvent for dimethylbenzene, the mass volume ratio of welan gum and reaction dissolvent is 60g/L.Welan gum and the molar ratio of citric acid are 6:
7.Citric acid is added in the suspension of welan gum and reaction dissolvent in 10min.Reaction temperature is 120 DEG C, the reaction time
For 12h.Speed of agitator is 500rpm, and modified welan gum product is made.
Embodiment 5：
It is same as Example 1, it differs only in：
The phase transfer catalyst is tetrabutylammonium bromide, and the mass ratio of welan gum and phase transfer catalyst is 2: 1.Instead
Answer solvent for chlorobenzene, the mass volume ratio of welan gum and reaction dissolvent is 70g/L.Welan gum and the molar ratio of citric acid are 3:
28.Citric acid is added in the suspension of welan gum and reaction dissolvent in 60min.Reaction speed of agitator is 550rpm, system
Welan gum product must be modified.
Comparative example 1：
Unmodified welan gum dissolves in 2wt%KCl solution 400mL, is not dissolved in 2h.Take unmodified welan gum
0.6wt% aqueous solutions are configured to, are measured under conditions of rotating speed is 300r/min using the fast rotational viscometer of ZNN-D6 types six viscous
Degree is 0.0415pa.s.
Claims (10)
1. a kind of preparation method of modified welan gum, which is characterized in that urge welan gum in acidulant, phase transfer with citrate
It is reacted in the presence of agent and reaction dissolvent, obtains modified welan gum.
2. according to the method described in claim 1, it is characterized in that, the citrate be citric acid sodium salt or sylvite,
Welan gum and the molar ratio of citrate are 6: 7~3: 28.
3. according to the method described in claim 1, it is characterized in that, the acidulant is hydrochloric acid.
4. according to the method described in claim 1, it is characterized in that, the phase transfer catalyst is benzyl triethyl ammonium chlorination
Ammonium, etamon chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, ten
One or more of dialkyl group trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, trimethyloctadecyl ammonium chloride, Wei
The mass ratio of blue glue and phase transfer catalyst is (1~2): 1.
5. according to the method described in claim 1, it is characterized in that, the aromatic hydrocarbon that reaction dissolvent is aromatic hydrocarbon, halogen replaces, water
One or more of, reaction temperature is 80~120 DEG C, and the reaction time is 6~12h.
6. according to the method described in claim 1, it is characterized in that, reaction dissolvent is benzene,toluene,xylene, chlorobenzene, dichloro
One or more of benzene, water.
7. according to the method described in claim 1, it is characterized in that, reaction carry out under agitation, speed of agitator be 450~
550rpm。
8. according to the method described in claim 1, it is characterized by comprising the following steps：
(1) saline citrate pH is first adjusted to 2~4 using acidulant, the saline citrate after being acidified；
(2) welan gum and the second reaction dissolvent are formed into suspension by phase transfer catalyst, then added in the suspension
Enter the saline citrate after the acidification that step (1) obtains, reacted, obtains modified welan gum.
9. according to the method described in claim 8, it is characterized in that, in step (1), a concentration of the 0.02 of saline citrate
~0.07g/mL.
10. the modification welan gum that the preparation method of the modification welan gum described in any one of claim 1~9 is prepared.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0520775A1 (en) * | 1991-06-28 | 1992-12-30 | Monsanto Company | Solution of welan gum in ethylene glycol |
| CN103570844A (en) * | 2013-11-20 | 2014-02-12 | 南京工业大学 | Preparation method for carboxyethyl welan gum |
| CN104151443A (en) * | 2014-08-13 | 2014-11-19 | 南京工业大学 | Preparation method of modified welan gum |
| CN105586026A (en) * | 2015-07-28 | 2016-05-18 | 陕西太昱科技发展有限公司 | Biologically recyclable biogum oil well fracturing fluid and preparation method thereof |
| CN110498867A (en) * | 2018-05-17 | 2019-11-26 | 中国石油化工股份有限公司 | Modified welan gum and preparation method thereof and aqueous fracturing fluid composition and aqueous fracturing fluid |
-
2018
- 2018-06-25 CN CN201810660307.2A patent/CN108641010B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0520775A1 (en) * | 1991-06-28 | 1992-12-30 | Monsanto Company | Solution of welan gum in ethylene glycol |
| CN103570844A (en) * | 2013-11-20 | 2014-02-12 | 南京工业大学 | Preparation method for carboxyethyl welan gum |
| CN104151443A (en) * | 2014-08-13 | 2014-11-19 | 南京工业大学 | Preparation method of modified welan gum |
| CN105586026A (en) * | 2015-07-28 | 2016-05-18 | 陕西太昱科技发展有限公司 | Biologically recyclable biogum oil well fracturing fluid and preparation method thereof |
| CN110498867A (en) * | 2018-05-17 | 2019-11-26 | 中国石油化工股份有限公司 | Modified welan gum and preparation method thereof and aqueous fracturing fluid composition and aqueous fracturing fluid |
Non-Patent Citations (3)
| Title |
|---|
| LI ZHONGWEI等: "Optimal experimental conditions for Welan gum production by support vector regression and adaptive genetic algorithm", 《PLOS ONE》 * |
| XIAOLIU LIU等: "Two-step economical welan gum production by Sphingomonas sp. HT-1 from sugar industrial by-products", 《CARBOHYDRATE POLYMERS》 * |
| 熊蓉春等: "相转移催化法合成羟丙基瓜尔胶", 《北京化工大学学报》 * |
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