CN112121860A - Vegetable gum oxidation degradation catalyst and preparation method thereof - Google Patents
Vegetable gum oxidation degradation catalyst and preparation method thereof Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/81—Amides; Imides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/16—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with inorganic material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/28—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic compounds containing nitrogen, sulfur or phosphorus
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/72—Manganese
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The invention discloses a vegetable gum oxidation degradation catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: the method comprises the following steps: preparing a diamide derivative by using o-phenylenediamine or an o-phenylenediamine derivative and picolinic acid through microwave heating in the presence of triethyl phosphite and a solvent; step two: the diamide derivative and manganese chloride are complexed in the presence of sodium alkoxide to form the vegetable gum oxidative degradation catalyst. The catalyst takes hydrogen peroxide as an oxidant to catalyze the degradation of 1, 4-glycosidic bond and 1, 6-glycosidic bond of guar gum, greatly reduces the viscosity of the guar gum, and can be used for degradation treatment of residual thickening agent recycled from the fracturing flowback fluid of the vegetable gum.
Description
Technical Field
The invention relates to a vegetable gum oxidation degradation catalyst and a preparation method thereof, belonging to the technical field of fine chemicals and oil-gas field development and environmental protection.
Background
The guar gum and the derivative thereof have good water solubility, and the jelly formed by crosslinking with boron has good sand carrying capacity, so the guar gum and the derivative thereof are widely used for water-based fracturing fluid sand carrying fluid for yield increase transformation of oil and gas fields, and a large amount of fracturing flowback fluid is generated after fracturing. Direct discharge not only pollutes the environment, but also wastes water resources, and the cost for concentrating to a treatment station for harmless treatment is high. The method is feasible and necessary, and can reduce waste water and water for liquid preparation, thereby achieving the effects of saving energy, reducing emission and reducing the fracturing cost.
In recent years, technical research on the recycling of the fracturing fluid and the oxidation residue thickener at home and abroad is carried out, and CN110898828A discloses a bentonite/BiWO 6 composite photocatalyst for treating polyacrylamide fracturing fluid;
CN109550517A discloses a catalytic oxidation composition for treating fracturing flow-back fluid, a method and application of the composition, wherein the catalytic oxidation composition is a catalyst prepared by copper oxide/nickel oxide loaded molecular sieve, hypochlorous acid is an oxidant, and COD is greatly reduced.
Disclosure of Invention
Aiming at the prior art, the invention provides a vegetable gum oxidative degradation catalyst and a preparation method thereof, which are inspired by iron-containing bio-enzyme, and utilize the characteristics of good selectivity and high catalytic efficiency of the bio-enzyme to synthesize a bionic iron-based compound, so that the catalyst with good selectivity on glycosidic bonds is expected to degrade guar macromolecules.
In order to achieve the purpose, the invention adopts the technical scheme that:
a vegetable gum oxidation degradation catalyst has the structure:
the preparation method of the vegetable gum oxidative degradation catalyst comprises the following steps: (1) mixing o-phenylenediamine or an o-phenylenediamine derivative with triethyl phosphite, adding picolinic acid dissolved in a solvent, carrying out condensation reaction, after the reaction is finished, evaporating the solvent under reduced pressure, washing with methanol to obtain a crude product, and recrystallizing to obtain a diamide derivative;
(2) performing coordination reaction between diamide derivative and manganese chloride in the presence of sodium alkoxide for 5-15min, filtering, washing with methanol water, and drying. Obtaining the vegetable gum oxidative degradation catalyst.
Wherein the materials for the reaction for preparing the diamide derivative in the first step are used as follows: o-phenylenediamine and its derivatives picolinic acid triethyl phosphite in a molar ratio of 1:2: 2; the solvent is pyridine, and the addition amount of the pyridine solvent is 10-12 times of the total mass of the pyridine solvent, the pyridine solvent and the solvent; the further o-phenylenediamine derivative is 4-methyl-1, 2-phenylenediamine.
Further, the condensation reaction condition is one of reaction at 60-80 ℃ for 1-5 hours or microwave heating at 200-350W for 5-15 min;
further, the recrystallization solvent is one of methanol and ethanol.
Further, the molar ratio of the reaction materials for preparing the vegetable gum oxidative degradation catalyst in the second step is as follows: diamide derivatives: MnCl2·4H2The molar ratio of the sodium alkoxide to the sodium alkoxide is 1:1:2, and the reaction solvent is one of methanol or ethanol.
Further, the method for degrading the vegetable gum oxidative degradation catalyst for the guar gum fracturing flowback fluid comprises the steps of adding the catalyst into the guar gum fracturing fluid, carrying out ultrasonic dispersion for 10min under stirring at 20-50 ℃, adding hydrogen peroxide with the volume ratio of 5 per mill to 10 per mill, carrying out ultrasonic reaction for 30-50min under stirring, and filtering out solids to obtain degraded filtrate.
The invention has the following excellent effects:
(1) the material is easy to obtain, and the preparation process is simple;
(2) high catalytic efficiency and good selectivity.
Detailed Description
The present invention will be further described with reference to the following examples.
The instruments, reagents, materials and the like used in the following examples are, unless otherwise specified, conventional instruments, reagents, materials and the like known in the art, and are commercially available, and the experimental methods, detection methods and the like used in the following examples are, unless otherwise specified, conventional experimental methods, detection methods and the like known in the art.
Drawings
FIG. 1 is a schematic diagram of the reaction process of the catalyst prepared in example 1.
Example 1
250ml of pyridine and 6.15g of picolinic acid were added to a three-necked flask, 2.7g of o-phenylenediamine and 8.6ml of triethyl phosphite were added with stirring, and the mixture was reacted at 75 ℃ for 4 hours, the solvent was distilled off under reduced pressure, the solid was washed with 50% aqueous methanol solution three times (15 ml. times.3 times), and vacuum-dried at 50 ℃ for 4 hours to obtain a crude product. 15g of the crude product was taken, and 300ml of methanol was added thereto, and the mixture was refluxed until the solid was dissolved, crystallized by slow cooling, filtered, washed with methanol (15 ml. times.3 times), and vacuum-dried at 50 ℃ for 4 hours to obtain 14.25g of the diamide derivative.
After 3.18g of the diamide derivative was added to 400ml of methanol (containing 1.08g of sodium methoxide), ultrasonic dispersion was carried out for 10min, 19.78g of MnCl2 & 4H2O was added, ultrasonic complexation reaction was carried out at room temperature for 10min, and the reaction was completed, followed by filtration, washing of the solid with 50% aqueous methanol (15 ml. times.3 times), and vacuum drying at 50 ℃ for 4 hours. 22.5g of a catalyst for oxidative degradation of a vegetable gum was obtained.
Example 2
250ml of pyridine and 6.15g of picolinic acid are added into a three-necked flask, 2.7g of o-phenylenediamine and 8.6ml of triethyl phosphite are added under stirring, microwave reaction is carried out for 10min (output power 220W and frequency 25HZ), after the reaction is finished, the solvent is evaporated under reduced pressure, the solid is washed three times (15ml multiplied by 3 times) with 50% methanol aqueous solution, and vacuum drying is carried out for 4 hours at 50 ℃ to obtain a crude product. 15g of the crude product was taken, and 300ml of methanol was added thereto, and the mixture was refluxed until the solid was dissolved, crystallized by slow cooling, filtered, washed with methanol (15 ml. times.3 times), and vacuum-dried at 50 ℃ for 4 hours to obtain 14.23g of the diamide derivative.
After 3.18g of the diamide derivative was added to 400ml of methanol (containing 1.08g of sodium methoxide), ultrasonic dispersion was carried out for 10min, 19.78g of MnCl2 & 4H2O was added, ultrasonic complexation reaction was carried out at room temperature for 10min, and the reaction was completed, followed by filtration, washing of the solid with 50% aqueous methanol (15 ml. times.3 times), and vacuum drying at 50 ℃ for 4 hours. 22.45g of the catalyst for oxidative degradation of vegetable gum was obtained.
Example 3
250ml of pyridine and 6.15g of picolinic acid are added into a three-necked flask, 2.7g of 4-methyl-1, 2-o-phenylenediamine and 8.6ml of triethyl phosphite are added under stirring, microwave reaction is carried out for 8min (output power 220W, frequency 25HZ), after the reaction is finished, the solvent is distilled off under reduced pressure, the solid is washed with 50% methanol aqueous solution for three times (15ml multiplied by 3 times), and vacuum drying is carried out for 3 hours at 60 ℃ to obtain a crude product. 15g of the crude product was taken, and 300ml of methanol was added thereto, and the mixture was refluxed until the solid was dissolved, crystallized by slow cooling, filtered, washed with methanol (15 ml. times.3 times), and vacuum-dried at 50 ℃ for 4 hours to obtain 14.18g of a diamide derivative.
After 3.18g of the diamide derivative was added to 400ml of methanol (containing 1.08g of sodium methoxide), ultrasonic dispersion was carried out for 5min, 19.78g of MnCl2 & 4H2O was added, ultrasonic complexation reaction was carried out at room temperature for 10min, and the reaction was completed, followed by filtration, solid washing with 50% aqueous methanol (15 ml. times.3 times) and vacuum drying at 50 ℃ for 4 hours. 22.48g of the catalyst for oxidative degradation of vegetable gum was obtained.
Example 4
Adding 1000ml of 0.3% hydroxypropyl guar gum aqueous solution into 2g of the catalyst in the example 2, ultrasonically dispersing for 10min at the temperature of 30 ℃ under stirring, adding 5ml of hydrogen peroxide, ultrasonically reacting for 30min under stirring, and filtering out solids to obtain No. 1 degradation filtrate.
Example 5
Adding 1000ml of 0.3% hydroxypropyl guar gum aqueous solution into 2g of the catalyst in the example 1, performing ultrasonic dispersion for 10min at the temperature of 30 ℃ under stirring, adding 5ml of hydrogen peroxide, performing ultrasonic reaction for 30min under stirring, and filtering out solids to obtain No. 2 degradation filtrate.
Example 6
Adding 1000ml of 0.3% hydroxypropyl guar gum aqueous solution into 2g of the catalyst in the embodiment 3, performing ultrasonic dispersion for 10min at the temperature of 20 ℃ under stirring, adding 7ml of hydrogen peroxide, performing ultrasonic reaction for 30min under stirring, and filtering out solids to obtain No. 3 degradation filtrate.
Example 7
Adding 1000ml of 0.3% hydroxypropyl guar gum aqueous solution into 1g of the catalyst in the example 2, performing ultrasonic dispersion for 10min at 20 ℃ under stirring, adding 8ml of hydrogen peroxide, performing ultrasonic reaction for 50min under stirring, and filtering out solids to obtain No. 4 degradation filtrate.
Example 8
Adding 1000ml of 0.3% hydroxypropyl guar gum aqueous solution into 5ml of hydrogen peroxide at 30 ℃, and performing ultrasonic reaction for 30min under stirring to obtain No. 1 control degradation filtrate.
Example 9
1000ml of 0.3% hydroxypropyl guar gum aqueous solution is taken, 0.3g of ammonium persulfate is added, and the temperature is kept at 80 ℃ for 4 hours to obtain 2# control degradation filtrate.
Examples of Oxidation Properties
And (3) taking 500mL of degradation liquid, evaluating the degradation degree by taking the microfiltration time and the liquid amount obtained by filtration as evaluation indexes, wherein the filtration time is long or the obtained liquid is little, and the degradation is poor due to more undegraded macromolecules in the system or small degradation degree. The filtration result of degradation liquid of examples 4 to 8 is shown in Table 1 by using a 0.1 micron filter membrane, 4KPa,600r/min, membrane flux and clear water of 35ml/min and filtration time of 3 min.
Table 1 examples of catalyst degradation of guar
| Example/degradation filtrate | Micro-filtration yield (ml) |
| 4/1 | 298 |
| 5/2 | 287 |
| 6/3 | 287 |
| 7/4 | 334 |
| 8/1# control degradation filtrate | 78 |
| 9/2# control degradation filtrate | 115 |
| 0.3% guar gum | 5.2 |
Claims (9)
1. The vegetable gum oxidation degradation catalyst is characterized in that the structural schematic diagram of the catalyst is as follows:
2. the method for preparing a catalyst for oxidative degradation of vegetable gums according to claim 1, wherein the preparation process comprises the steps of:
(1) the method comprises the following steps: mixing o-phenylenediamine or o-phenylenediamine derivatives with triethyl phosphite, adding picolinic acid dissolved in pyridine, performing condensation reaction, after the reaction is finished, distilling under reduced pressure to remove a solvent, washing with methanol to obtain a crude product, and recrystallizing to obtain a diamide derivative;
(2) step two: suspending the diamide derivative in an alcoholic solution of sodium alkoxide, performing ultrasonic dispersion, adding manganese chloride, performing ultrasonic reaction at room temperature for 5-15min, filtering, washing with a methanol aqueous solution, and drying to obtain the catalyst for oxidative degradation of the vegetable gum.
3. The method for preparing the catalyst for oxidative degradation of vegetable gum according to claim 2, wherein the molar ratio of the reaction materials for preparing the diamide derivative in the first step is as follows: o-phenylenediamine or o-phenylenediamine derivatives, picolinic acid triethyl phosphite 1:2: 2; the addition amount of the pyridine is 10-12 times of the total mass of the three.
4. The method for preparing a catalyst for oxidative degradation of vegetable gums according to claim 2, wherein the o-phenylenediamine derivative is 4-methyl-1, 2-phenylenediamine.
5. The method for preparing the catalyst for oxidative degradation of vegetable gum according to claim 2, wherein the condensation reaction is a reaction at 60-80 ℃ for 1-5 hours or a microwave heating at 200-350W for 5-15 min.
6. The method for preparing a catalyst for oxidative degradation of vegetable gum as claimed in claim 2, wherein the recrystallization solvent is one of methanol or ethanol.
7. The method of claim 2, wherein the alcohol solution is one of methanol and ethanol, and the sodium alkoxide is one of sodium methoxide and sodium ethoxide.
8. The method for preparing the catalyst for oxidative degradation of vegetable gum according to claim 2, wherein the molar ratio of the reaction materials for preparing the catalyst for oxidative degradation of vegetable gum in the second step is: diamide derivatives: MnCl2·4H2O is 1:1:2 of sodium alkoxide.
9. The method for the degradation treatment of the guar fracturing flowback fluid by using the vegetable gum oxidative degradation catalyst as claimed in any one of claims 1 to 8, wherein the use method comprises the steps of adding the catalyst into the guar fracturing fluid, carrying out ultrasonic dispersion for 10min under stirring at 20-50 ℃, adding hydrogen peroxide with the volume ratio of 5 per mill to 10 per mill, carrying out ultrasonic reaction for 30-50min under stirring, and filtering out solids to obtain a degradation filtrate.
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| US20140323713A1 (en) * | 2013-04-24 | 2014-10-30 | David S. Karpovich | Bio-degradable material and method |
| CN103480419A (en) * | 2013-09-24 | 2014-01-01 | 陕西省石油化工研究设计院 | Selective high-molecular fracture catalyst as well as preparation method and application thereof |
| CN105819630A (en) * | 2016-05-26 | 2016-08-03 | 中国石油集团川庆钻探工程有限公司长庆井下技术作业公司 | Flowback plant-gum fracturing liquid treating technology |
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