CN110407331A - A kind of preparation method of green sustained release antisludging agent - Google Patents
A kind of preparation method of green sustained release antisludging agent Download PDFInfo
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- CN110407331A CN110407331A CN201910506067.5A CN201910506067A CN110407331A CN 110407331 A CN110407331 A CN 110407331A CN 201910506067 A CN201910506067 A CN 201910506067A CN 110407331 A CN110407331 A CN 110407331A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/342—Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the enzymes used
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
- C02F5/145—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus combined with inorganic substances
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
- C12N11/08—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer
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- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
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- C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
- C12N9/14—Hydrolases (3)
- C12N9/24—Hydrolases (3) acting on glycosyl compounds (3.2)
- C12N9/2402—Hydrolases (3) acting on glycosyl compounds (3.2) hydrolysing O- and S- glycosyl compounds (3.2.1)
- C12N9/2405—Glucanases
- C12N9/2408—Glucanases acting on alpha -1,4-glucosidic bonds
- C12N9/2411—Amylases
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- C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
- C12N9/14—Hydrolases (3)
- C12N9/48—Hydrolases (3) acting on peptide bonds (3.4)
- C12N9/50—Proteinases, e.g. Endopeptidases (3.4.21-3.4.25)
- C12N9/64—Proteinases, e.g. Endopeptidases (3.4.21-3.4.25) derived from animal tissue
- C12N9/6402—Proteinases, e.g. Endopeptidases (3.4.21-3.4.25) derived from animal tissue from non-mammals
- C12N9/6405—Proteinases, e.g. Endopeptidases (3.4.21-3.4.25) derived from animal tissue from non-mammals not being snakes
- C12N9/641—Cysteine endopeptidases (3.4.22)
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention
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- C12Y—ENZYMES
- C12Y304/00—Hydrolases acting on peptide bonds, i.e. peptidases (3.4)
- C12Y304/22—Cysteine endopeptidases (3.4.22)
- C12Y304/22002—Papain (3.4.22.2)
Abstract
The present invention relates to a kind of preparation methods of green sustained release antisludging agent, belong to additive technology field.The invention firstly uses sodium metaperiodates to be modified starch, form it into aldehyde radical, then ball milling modification is carried out with surfactant again, improve stability in hard water, and modified starch activity can be increased by ball milling, the 3-aminopropyltriethoxysilane in surfactant, which is decomposed, simultaneously generates silicon oxygen bond, make modified starch combination silicon oxygen bond, increase the binding performance with substrate, again with butyl acrylate, acrylamide carries out graft reaction, additive is added simultaneously and introduces active body, increase and calcium ion etc. are combined, it can be very good simultaneously using active body and maleic anhydride, ammonium hydroxide etc. carries out hybrid reaction, cooperate mixed enzyme, decomposition using enzyme to starch, the substances such as the calcium ion of deposition can be made slowly to be detached from substrate, and used raw material is degradable, it is big to efficiently solve current antisludging agent toxicity, easily cause environment The problem of pollution.
Description
Technical field
The present invention relates to a kind of preparation methods of green sustained release antisludging agent, belong to additive technology field.
Background technique
Antisludging agent be with can slightly solubility inorganic salts in disperse water, inhibit or interfere with slightly solubility inorganic salts in metal surface
Precipitating, fouling function, and metal equipment is maintained to have a kind of medicament of good heat-transfer effect.It is increasingly short due to freshwater resources
Lack, industrial circulating water cooling treatment medicament is increasingly valued by people, recirculated cooling water along with production overall process,
Account for the 70~80% of total water consumption.In the industrial production, cooling is carried out to equipment frequently with recirculated water or heat is transmitted.Recirculated water
Because its in systems can evaporation section vapor so that the salinity in system increases, and the salt water of high concentration with steel,
The problem of fouling or corrosion are easy to appear in equipment, pipeline based on steel structure, in recirculating cooling water system operational process,
Fouling can have serious consequences to production, reduce heat exchange efficiency, or even cause to stop work, and bring greatly economic damage to industrial production
It loses.To slow down fouling, so that cooling water system effectively, is steadily run, Scale Inhibitors for Water is added in cooling water, be one
The both economical of kind is also common method.
Industrially common form mainly has corrosion inhibiter and two kinds of dispersing agent to antisludging agent, and corrosion inhibiter mainly has with lower class
Type: inorganic polymeric phosphate, organic multicomponent phosphoric acid, gluconic acid and tannic acid etc. mostly use phosphorus line formulation in circulation,
Wherein most are organic multicomponent phosphonic acids, for example, 1-hydroxy ethylidene-1,1-diphosphonic acid (HDPE), aminotrimethylenephosphonic acid (ATMP),
Ethylene diamine tetra methylene phosphonic acid (EDTMP) etc..Dispersing agent be mainly in, the water-soluble polymer of low relative molecular mass, including it is equal
Polymers and copolymer two major classes, wherein homopolymer has polyacrylic acid and its sodium salt, hydrolysis of polymaleic anhydride etc., and homopolymer is due to it
The limitation of structure, dispersing and antisludging ability is also limited, and the kind of copolymer is then more, with the two of acrylic acid series and maleic acid system
Based on member or terpolymer, though substantially increasing dispersing and antisludging ability, corrosion inhibition is relatively poor.
At present usually using originals such as inorganic polyphosphate, organic phosphoric acid, phosphorus carboxylic acid, nitrite, zinc salt and molybdates
Material is used as antisludging agent.Although there is certain effect using above-mentioned antisludging agent, but there is also some problems in actual use: antisludging agent
Contain nitrite, molybdate in constituent for noxious material, is not only hazardous to the human body, pollution will also result in environment.
Therefore, the antisludging agent for producing a kind of nontoxic pollution is extremely urgent.
Summary of the invention
The technical problems to be solved by the invention: for the problem that current antisludging agent toxicity is big, easily causing environmental pollution, this
Invention provides a kind of preparation method of green sustained release antisludging agent.
In order to solve the above technical problems, the present invention is using technical solution as described below:
A kind of preparation method of green sustained release antisludging agent, the preparation method include the following steps:
(1) starch, mixed solvent 1:8~10 in mass ratio are uniformly mixed, are heated to 60~70 DEG C, add starch quality 10
~15% modifying agent heats up, cooling, stands, and dried object is collected in spray drying；
(2) dried object, surfactant and water 13~15:2:2 in mass ratio~5 are subjected to ball milling, collect ball milling object, by weight
Number meter, take 100~150 parts of water, 70~80 parts of dimethylformamides, 30~40 parts of ball milling objects, 13~15 parts of butyl acrylates,
10~12 parts of acrylamides, 3~6 parts of additives, 1~3 part of initiator；
(3) water, dimethylformamide, ball milling object, butyl acrylate, acrylamide are put into reaction kettle, using nitrogen protection,
Preheating, adds additive, initiator, heats up, is stirred to react, and cools down, discharges while hot, is freeze-dried, and collects freeze-drying object；
(4) freeze-drying object, ammonium hydroxide and maleic anhydride 4~7:13 in mass ratio~16:1~3 are mixed, at 180~190 DEG C,
Stirring, is cooled to room temperature, adds the mixed enzyme of lyophilized substance amount 8~12%, stir evenly, and is freeze-dried, and washs, and does
It is dry to get green sustained release antisludging agent.
Mixed solvent is ethanol solution in the step (1), 9~11:5 is mixed glycerol by volume.
Modifying agent is citric acid in the step (1), sodium metaperiodate 3~7:4 in mass ratio is mixed.
Surfactant is 3-aminopropyltriethoxysilane in the step (2), Cocoamidopropyl betaine is pressed
Mass ratio 1:3~5 mix.
The additive is vinyl acetic acid, any one in maleic anhydride.
The initiator is sodium peroxydisulfate, potassium permanganate 3:1~3 in mass ratio mix.
In the step (4) load enzyme the preparation method comprises the following steps:
A. mixture, water and the adjuvant ultrasonic vibration of 5~7:13:1 in mass ratio are stood using pH to 2.5~3.0 is adjusted,
It reuses sodium hydroxide solution and adjusts pH to 13, the sodium bicarbonate of mixture quality 3~5% is added, heated at 80~90 DEG C；
B. cooling after heating, it discharges, filters, it is dry, dried object is collected, by dried object and water 2:5~7 in mass ratio
It is mixed, adjusts pH to 8.0 using sodium hydroxide solution, stand, filter residue is collected in filtering, and washing is collected in washing to neutrality
Object；
C. washings, addition enzyme, polyglutamic acid, water 2:4~6:3:13 in mass ratio are uniformly mixed, are stood, freeze-drying, i.e.,
Enzyme must be loaded.
Mixture is ferric nitrate in the step A, ferrous nitrate 4:2~5 in mass ratio are uniformly mixed to get metal salt.
In the step A adjuvant be butyl titanate, titanium chloride by etc. mass mixings form.
It is to mix amylase, papain 3:2~4 in mass ratio that enzyme is added in the step C.
The present invention is compared with other methods, and advantageous effects are:
The invention firstly uses sodium metaperiodates to be modified starch, forms it into aldehyde radical, then carries out with surfactant again
Ball milling modification improves stability in hard water, and can increase modified starch activity, while the 3- ammonia in surfactant by ball milling
Base propyl-triethoxysilicane, which decomposes, generates silicon oxygen bond, makes modified starch combination silicon oxygen bond, increases the binding performance with substrate,
Carry out graft reaction with butyl acrylate, acrylamide again, while additive be added and introduces active body, increase with calcium ion etc. into
Row combines, while can be very good to form polyglutamic acid with progress hybrid reactions such as maleic anhydride, ammonium hydroxide using active body, and
Make modified starch grafted polyglutamic acid, further increase scale inhibition efficiency, cooperate mixed enzyme, the decomposition using enzyme to starch can be with
The substances such as the calcium ion of deposition are made slowly to be detached from substrate, and used raw material is degradable, efficiently solves current antisludging agent
The problem of toxicity is big, easily causes environmental pollution.
Specific embodiment
Mixed solvent is 1.2mol/L ethanol solution, 9~11:5 is mixed glycerol by volume.
Modifying agent is citric acid, sodium metaperiodate 3~7:4 in mass ratio is mixed.
Surfactant is 3-aminopropyltriethoxysilane, Cocoamidopropyl betaine 1:3~5 in mass ratio are mixed
It closes.
Additive is vinyl acetic acid, any one in maleic anhydride.
Initiator is sodium peroxydisulfate, potassium permanganate 3:1~3 in mass ratio mix.
Mixture is ferric nitrate, ferrous nitrate 4:2~5 in mass ratio are uniformly mixed to get metal salt.
Adjuvant be butyl titanate, titanium chloride by etc. mass mixings form.
Addition enzyme is to mix amylase, papain 3:2~4 in mass ratio.
Load enzyme the preparation method comprises the following steps:
A. by mixture, water and adjuvant the ultrasonic vibration 10min of 5~7:13:1 in mass ratio, using adjusting pH to 2.5~3.0,
3h is stood, sodium hydroxide solution is reused and adjusts pH to 13, the sodium bicarbonate of mixture quality 3~5% is added, at 80~90 DEG C
Heat 5h；
B. it after heating, is cooled to room temperature, discharges, filtration cakes torrefaction is collected dried object, dried object and water are pressed by filtering
Mass ratio 2:5~7 are mixed, and adjust pH to 8.0 using sodium hydroxide solution, stand 2h, and filter residue is collected in filtering, and washing is extremely
Neutrality collects washings；
C. washings, addition enzyme, polyglutamic acid, water 2:4~6:3:13 in mass ratio are uniformly mixed, stand 3h, is freeze-dried,
Up to load enzyme.
A kind of preparation method of green sustained release antisludging agent, the preparation method include the following steps:
(1) starch, mixed solvent 1:8~10 in mass ratio are uniformly mixed, are heated to 60~70 DEG C, add starch quality 10
~15% modifying agent is warming up to 100~105 DEG C, keeps the temperature 2~4h, is cooled to room temperature, and stands 1h, and drying is collected in spray drying
Object；
(2) dried object, surfactant and water 13~15:2:2~5 in mass ratio are subjected to ball milling 50min with 600r/min, received
Collect ball milling object, according to parts by weight, take 100~150 parts of water, 70~80 parts of dimethylformamides, 30~40 parts of ball milling objects, 13~
15 parts of butyl acrylates, 10~12 parts of acrylamides, 3~6 parts of additives, 1~3 part of initiator；
(3) water, dimethylformamide, ball milling object, butyl acrylate, acrylamide are put into reaction kettle, using nitrogen protection,
In 60 DEG C of preheating 50min, additive, initiator are added, 105~110 DEG C is warming up to, is stirred to react 5h, be cooled to 50~60
DEG C, it discharges, is freeze-dried while hot, collect freeze-drying object；
(4) freeze-drying object, 1.1mol/L ammonium hydroxide and maleic anhydride 4~7:13 in mass ratio~16:1~3 are mixed, 180
~190 DEG C, 3~5h is stirred, is cooled to room temperature, is added the mixed enzyme of lyophilized substance amount 8~12%, stir evenly, it is cold
Dry, collection dried object is lyophilized, washs dried object using dehydrated alcohol, it is dry to get green sustained release antisludging agent.
Embodiment 1
Mixture is ferric nitrate, ferrous nitrate 4:2 in mass ratio is uniformly mixed to get metal salt.
Adjuvant be butyl titanate, titanium chloride by etc. mass mixings form.
Addition enzyme is to mix amylase, papain 3:2 in mass ratio.
Load enzyme the preparation method comprises the following steps:
A. mixture, water and adjuvant 5:13:1 ultrasonic vibration 10min in mass ratio are stood into 3h using pH to 2.5 is adjusted,
It reuses sodium hydroxide solution and adjusts pH to 13, the sodium bicarbonate of mixture quality 3% is added, in 80 DEG C of heating 5h；
B. it after heating, is cooled to room temperature, discharges, filtration cakes torrefaction is collected dried object, dried object and water are pressed by filtering
Mass ratio 2:5 is mixed, and adjusts pH to 8.0 using sodium hydroxide solution, stands 2h, and filter residue is collected in filtering, is washed into
Property, collect washings；
C. washings, addition enzyme, polyglutamic acid, water 2:4:3:13 in mass ratio are uniformly mixed, stand 3h, is freeze-dried, i.e.,
Enzyme must be loaded.
In addition load enzyme can also be carried out directly using addition enzyme using effect is equal.
Mixed solvent is 1.2mol/L ethanol solution, 11:5 is mixed glycerol by volume.
Modifying agent is citric acid, sodium metaperiodate 7:4 in mass ratio is mixed.
Surfactant is 3-aminopropyltriethoxysilane, Cocoamidopropyl betaine 1:5 in mass ratio mixing
It forms.
Additive is vinyl acetic acid.
Initiator is sodium peroxydisulfate, potassium permanganate 3:3 in mass ratio is mixed.
A kind of preparation method of green sustained release antisludging agent, the preparation method include the following steps:
(1) starch, mixed solvent 1:10 in mass ratio are uniformly mixed, are heated to 70 DEG C, add changing for starch quality 15%
Property agent, be warming up to 105 DEG C, keep the temperature 4h, be cooled to room temperature, stand 1h, dried object is collected in spray drying；
(2) dried object, surfactant and water 15:2:5 in mass ratio are subjected to ball milling 50min with 600r/min, collect ball milling
Object takes 150 parts of water, 80 parts of dimethylformamides, 40 parts of ball milling objects, 15 parts of butyl acrylates, 12 parts of propylene according to parts by weight
Amide, 6 parts of additives, 3 parts of initiators；
(3) water, dimethylformamide, ball milling object, butyl acrylate, acrylamide are put into reaction kettle, using nitrogen protection,
In 60 DEG C of preheating 50min, additive, initiator are added, 110 DEG C is warming up to, is stirred to react 5h, 60 DEG C is cooled to, goes out while hot
Freeze-drying object is collected in material, freeze-drying；
(4) freeze-drying object, 1.1mol/L ammonium hydroxide and maleic anhydride 7:16:3 in mass ratio are mixed, at 190 DEG C, stir 5h,
It is cooled to room temperature, adds the mixed enzyme of lyophilized substance amount 12%, stir evenly, be freeze-dried, collect dried object, use
Dehydrated alcohol washs dried object, dry to get green sustained release antisludging agent.
Embodiment 2
Mixed solvent is 1.2mol/L ethanol solution, 10:5 is mixed glycerol by volume.
Modifying agent is citric acid, sodium metaperiodate 5:4 in mass ratio is mixed.
Surfactant is 3-aminopropyltriethoxysilane, Cocoamidopropyl betaine 1:4 in mass ratio mixing
It forms.
Additive is maleic anhydride.
Initiator is sodium peroxydisulfate, potassium permanganate 3:2 in mass ratio is mixed.
Mixture is ferric nitrate, ferrous nitrate 4:3 in mass ratio is uniformly mixed to get metal salt.
Adjuvant be butyl titanate, titanium chloride by etc. mass mixings form.
Addition enzyme is to mix amylase, papain 3:3 in mass ratio.
Load enzyme the preparation method comprises the following steps:
A. mixture, water and adjuvant 6:13:1 ultrasonic vibration 10min in mass ratio are stood into 3h using pH to 2.5 is adjusted,
It reuses sodium hydroxide solution and adjusts pH to 13, the sodium bicarbonate of mixture quality 4% is added, in 85 DEG C of heating 5h；
B. it after heating, is cooled to room temperature, discharges, filtration cakes torrefaction is collected dried object, dried object and water are pressed by filtering
Mass ratio 2:6 is mixed, and adjusts pH to 8.0 using sodium hydroxide solution, stands 2h, and filter residue is collected in filtering, is washed into
Property, collect washings；
C. washings, addition enzyme, polyglutamic acid, water 2:5:3:13 in mass ratio are uniformly mixed, stand 3h, is freeze-dried, i.e.,
Enzyme must be loaded.
In addition load enzyme can also be carried out directly using addition enzyme using effect is equal.
A kind of preparation method of green sustained release antisludging agent, the preparation method include the following steps:
(1) starch, mixed solvent 1:9 in mass ratio are uniformly mixed, are heated to 65 DEG C, add the modification of starch quality 13%
Agent is warming up to 103 DEG C, keeps the temperature 3h, is cooled to room temperature, and stands 1h, and dried object is collected in spray drying；
(2) dried object, surfactant and water 14:2:3 in mass ratio are subjected to ball milling 50min with 600r/min, collect ball milling
Object takes 130 parts of water, 75 parts of dimethylformamides, 35 parts of ball milling objects, 14 parts of butyl acrylates, 11 parts of propylene according to parts by weight
Amide, 5 parts of additives, 2 parts of initiators；
(3) water, dimethylformamide, ball milling object, butyl acrylate, acrylamide are put into reaction kettle, using nitrogen protection,
In 60 DEG C of preheating 50min, additive, initiator are added, 108 DEG C is warming up to, is stirred to react 5h, 55 DEG C is cooled to, goes out while hot
Freeze-drying object is collected in material, freeze-drying；
(4) freeze-drying object, 1.1mol/L ammonium hydroxide and maleic anhydride 6:15:2 in mass ratio are mixed, at 185 DEG C, stir 4h,
It is cooled to room temperature, adds the mixed enzyme of lyophilized substance amount 10%, stir evenly, be freeze-dried, collect dried object, use
Dehydrated alcohol washs dried object, dry to get green sustained release antisludging agent.
Embodiment 3
Mixed solvent is 1.2mol/L ethanol solution, 9:5 is mixed glycerol by volume.
Modifying agent is citric acid, sodium metaperiodate 3:4 in mass ratio is mixed.
Surfactant is 3-aminopropyltriethoxysilane, Cocoamidopropyl betaine 1:3 in mass ratio mixing
It forms.
Additive is vinyl acetic acid.
Initiator is sodium peroxydisulfate, potassium permanganate 3:1 in mass ratio is mixed.
Mixture is ferric nitrate, ferrous nitrate 4:5 in mass ratio is uniformly mixed to get metal salt.
Adjuvant be butyl titanate, titanium chloride by etc. mass mixings form.
Addition enzyme is to mix amylase, papain 3:4 in mass ratio.
Load enzyme the preparation method comprises the following steps:
A. mixture, water and adjuvant 7:13:1 ultrasonic vibration 10min in mass ratio are stood into 3h using pH to 3.0 is adjusted,
It reuses sodium hydroxide solution and adjusts pH to 13, the sodium bicarbonate of mixture quality 3~5% is added, in 90 DEG C of heating 5h；
B. it after heating, is cooled to room temperature, discharges, filtration cakes torrefaction is collected dried object, dried object and water are pressed by filtering
Mass ratio 2:7 is mixed, and adjusts pH to 8.0 using sodium hydroxide solution, stands 2h, and filter residue is collected in filtering, is washed into
Property, collect washings；
C. washings, addition enzyme, polyglutamic acid, water 2:6:3:13 in mass ratio are uniformly mixed, stand 3h, is freeze-dried, i.e.,
Enzyme must be loaded.
A kind of preparation method of green sustained release antisludging agent, the preparation method include the following steps:
(1) starch, mixed solvent 1:8 in mass ratio are uniformly mixed, are heated to 60 DEG C, add the modification of starch quality 10%
Agent is warming up to 100 DEG C, keeps the temperature 2h, is cooled to room temperature, and stands 1h, and dried object is collected in spray drying；
(2) dried object, surfactant and water 13:2:2 in mass ratio are subjected to ball milling 50min with 600r/min, collect ball milling
Object takes 100 parts of water, 70 parts of dimethylformamides, 30 parts of ball milling objects, 13 parts of butyl acrylates, 10 parts of propylene according to parts by weight
Amide, 3 parts of additives, 1 part of initiator；
(3) water, dimethylformamide, ball milling object, butyl acrylate, acrylamide are put into reaction kettle, using nitrogen protection,
In 60 DEG C of preheating 50min, additive, initiator are added, 105 DEG C is warming up to, is stirred to react 5h, 50 DEG C is cooled to, goes out while hot
Freeze-drying object is collected in material, freeze-drying；
(4) freeze-drying object, 1.1mol/L ammonium hydroxide and maleic anhydride 4:13:1 in mass ratio are mixed, at 180 DEG C, stir 3h,
It is cooled to room temperature, adds the mixed enzyme of lyophilized substance amount 8%, stir evenly, be freeze-dried, collect dried object, use
Dehydrated alcohol washs dried object, dry to get green sustained release antisludging agent.
Comparative example 1
It is substantially the same manner as Example 2, only the difference is that lacking the mixed enzyme in step (4).
Comparative example 2
Commercially available antisludging agent.
The antisludging agent of antisludging agent obtained by examples detailed above and reference examples is detected, specific detection is as follows:
The antisludging agent of the antisludging agent of embodiment preparation and reference examples is subjected to antisludging test, with anhydrous calcium chloride and sodium bicarbonate
Prepare Ca2 +And HCO3 -Mass concentration is respectively the water sample of 315mg/L and 803mg/L, is separately added into the scale inhibition of embodiment preparation
The antisludging agent of agent and reference examples, setting experimental temperature are 70 ± 5 DEG C, and 10h is placed in water bath with thermostatic control, is adopted after precipitation of calcium carbonate is complete
With EDTA compleximetry, remaining Ca in test solution is titrated+The amount of the substance of consumed EDTA is Ca+Substance amount.Tool
Body carries out calcium carbonate referring to the method in " the measurement tosca methods of water treatment agent scale-inhibiting properties " (GB/T 16632-2008)
Scale inhibition performance experiment, and scale inhibition performance is calculated separately, while the scale inhibition efficiency after detection 1 day, the results are shown in Table 1.
Table 1:
| Test item | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| 10mg/L antisludging agent scale inhibition performance % is added | 98.2 | 98.9 | 98.1 | 97.2 | 89.6 |
| 5mg/L antisludging agent scale inhibition performance % is added | 97.8 | 98.6 | 96.9 | 95.8 | 64.7 |
| Addition 10mg/L scale inhibition performance (%) after 1 day | 79.3 | 81.2 | 80.9 | 65.2 | 52.3 |
It can to sum up obtain, green sustained release antisludging agent prepared by the present invention has preferable scale inhibition effect.
Claims (10)
1. a kind of preparation method of green sustained release antisludging agent, which is characterized in that the preparation method includes the following steps:
(1) starch, mixed solvent 1:8~10 in mass ratio are uniformly mixed, are heated to 60~70 DEG C, add starch quality 10
~15% modifying agent heats up, cooling, stands, and dried object is collected in spray drying；
(2) dried object, surfactant and water 13~15:2:2 in mass ratio~5 are subjected to ball milling, collect ball milling object, by weight
Number meter, take 100~150 parts of water, 70~80 parts of dimethylformamides, 30~40 parts of ball milling objects, 13~15 parts of butyl acrylates,
10~12 parts of acrylamides, 3~6 parts of additives, 1~3 part of initiator；
(3) water, dimethylformamide, ball milling object, butyl acrylate, acrylamide are put into reaction kettle, using nitrogen protection,
Preheating, adds additive, initiator, heats up, is stirred to react, and cools down, discharges while hot, is freeze-dried, and collects freeze-drying object；
(4) freeze-drying object, ammonium hydroxide and maleic anhydride 4~7:13 in mass ratio~16:1~3 are mixed, at 180~190 DEG C,
Stirring, is cooled to room temperature, adds the load enzyme of lyophilized substance amount 8~12%, stir evenly, and is freeze-dried, and washs, and does
It is dry to get green sustained release antisludging agent.
2. the preparation method of green sustained release antisludging agent according to claim 1, which is characterized in that mixing in the step (1)
Solvent is ethanol solution, 9~11:5 is mixed glycerol by volume.
3. the preparation method of green sustained release antisludging agent according to claim 1, which is characterized in that modified in the step (1)
Agent is citric acid, sodium metaperiodate 3~7:4 in mass ratio is mixed.
4. the preparation method of green sustained release antisludging agent according to claim 1, which is characterized in that surface in the step (2)
Activating agent is 3-aminopropyltriethoxysilane, Cocoamidopropyl betaine 1:3~5 in mass ratio mix.
5. the preparation method of green sustained release antisludging agent according to claim 1, which is characterized in that the additive is vinyl
Any one in acetic acid, maleic anhydride.
6. the preparation method of green sustained release antisludging agent according to claim 1, which is characterized in that the initiator is persulfuric acid
Sodium, potassium permanganate 3:1~3 in mass ratio mix.
7. the preparation method of green sustained release antisludging agent according to claim 1, which is characterized in that load in the step (4)
Enzyme the preparation method comprises the following steps:
A. mixture, water and the adjuvant ultrasonic vibration of 5~7:13:1 in mass ratio are stood using pH to 2.5~3.0 is adjusted,
It reuses sodium hydroxide solution and adjusts pH to 13, the sodium bicarbonate of mixture quality 3~5% is added, heated at 80~90 DEG C；
B. cooling after heating, it discharges, filters, it is dry, dried object is collected, by dried object and water 2:5~7 in mass ratio
It is mixed, adjusts pH to 8.0 using sodium hydroxide solution, stand, filter residue is collected in filtering, and washing is collected in washing to neutrality
Object；
C. washings, addition enzyme, polyglutamic acid, water 2:4~6:3:13 in mass ratio are uniformly mixed, are stood, freeze-drying, i.e.,
Enzyme must be loaded.
8. the preparation method of green sustained release antisludging agent according to claim 7, which is characterized in that mixture in the step A
It is uniformly mixed for ferric nitrate, ferrous nitrate 4:2~5 in mass ratio to get metal salt.
9. the preparation method of green sustained release antisludging agent according to claim 7, which is characterized in that adjuvant in the step A
For butyl titanate, titanium chloride by etc. mass mixings form.
10. the preparation method of green sustained release antisludging agent according to claim 7, which is characterized in that add enzyme in the step C
For amylase, papain 3:2~4 in mass ratio are mixed.
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| CN117820549A (en) * | 2024-03-01 | 2024-04-05 | 西南石油大学 | Scale inhibitor for oil and gas field injection, preparation method and application thereof |
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