CN105753182A - Styrene ketone-maleic anhydride-butadiene-butenol scale inhibitor and preparation method thereof - Google Patents

Styrene ketone-maleic anhydride-butadiene-butenol scale inhibitor and preparation method thereof Download PDF

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Publication number
CN105753182A
CN105753182A CN201610129742.3A CN201610129742A CN105753182A CN 105753182 A CN105753182 A CN 105753182A CN 201610129742 A CN201610129742 A CN 201610129742A CN 105753182 A CN105753182 A CN 105753182A
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CN
China
Prior art keywords
butadiene
butenol
maleic anhydride
preparation
styrene ketone
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Pending
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CN201610129742.3A
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Chinese (zh)
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不公告发明人
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Foshan Jucheng Biochemical Technology Research and Development Co Ltd
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Foshan Jucheng Biochemical Technology Research and Development Co Ltd
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Priority to CN201610129742.3A priority Critical patent/CN105753182A/en
Publication of CN105753182A publication Critical patent/CN105753182A/en
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00Specific treatment goals
    • C02F2303/22Eliminating or preventing deposits, scale removal, scale prevention

Abstract

The invention relates to a styrene ketone-maleic anhydride-butadiene-butenol scale inhibitor and a preparation method thereof.The preparation method is characterized by including mixing styrene ketone, maleic anhydride, butadiene and butenol in a molar ratio of 1: (1-10):(3-16):(4-20), and adding an initiator, a solvent and a catalyst into a reactor for copolymerization to obtain a yellow solid; dissolving the yellow solid in dimethyl fumarate, precipitating in ethyl ether, filtering, drying and grinding so as to obtain the styrene ketone-maleic anhydride-butadiene-butenol scale inhibitor.The styrene ketone-maleic anhydride-butadiene-butenol scale inhibitor prepared by the preparation method is high in scale inhibiting rate and biodegradation rate.

Description

The preparation method of a kind of styrene ketone-maleic anhydride-butadiene-butenol antisludging agent and prepared Antisludging agent
Technical field
The present invention relates to antisludging agent field, be specifically related to a kind of a kind of styrene ketone-maleic anhydride- The preparation method of butadiene-butenol antisludging agent and prepared antisludging agent.
Background technology
Antisludging agent be have can slightly solubility inorganic salts in disperse water, inhibit or interfere with slightly solubility without The machine salt precipitation in metal surface, fouling function, and maintain hardware to have good heat transfer to imitate The one class medicament of fruit.
Chinese patent CN102874938A discloses a kind of Phosphoric acid equipment pipeline scale inhibitor, relates to Antiscale field.Its main component and weight/mass percentage composition be: neopelex 0.5~ 1%, odium stearate 0.3~0.8%, sodium lignin sulfonate 1~2.5%, Sodium Polyacrylate 1.5~2%.After antisludging agent is heated to during use the temperature of 20~80 DEG C, add phosphate equipment In pipeline.The addition of antisludging agent is the 0.03%-0.05% of phosphoric acid by wet process.Use this antisludging agent, The Phosphoric Acid Concentration system cycle of operation extends, and shortens scavenging period, improves the operation ratio of device, And the temperature applicable range of this antisludging agent is wider compared with prior art, there is the biggest using value.
Chinese patent CN103833148A discloses one and the present invention relates to a kind of high efficiency composition Scale inhibitor, belongs to industrial water conditioning agent design field, it is characterised in that by terpolymer Barium-strontium scale inhibitor and bipolymer calcium scale inhibitor are compounding by mass percentage to be formed, wherein The mass percent of each component is: bipolymer calcium scale inhibitor: 25--75%;Ternary is altogether Polymers barium-strontium scale inhibitor: 25--75%;Described bipolymer calcium scale inhibitor is epoxy Butanedioic acid and the copolymer of ALS;Described terpolymer barium-strontium scale inhibitor is Acrylic or methacrylic acid and the copolymer of acrylate is added in maleic anhydride.This scale inhibition In the formula of agent the most phosphorous, during use, do not result in body eutrophication, to environment friend Good, it is adaptable to calcic, the isoionic water body of barium strontium, preparation method is simple, cost is relatively low, anti- Salt performance is good, good stability, applicability wide, more single terpolymer barium under equal dosage The scale inhibition effect of strontium antisludging agent or bipolymer calcium scale inhibitor is good.
Traditional antisludging agent exist scale inhibition performance low and degraded difficulty etc. shortcoming, therefore need exploitation one badly Plant excellent antisludging agent.
Summary of the invention
In order to solve the problems referred to above that prior art exists, the invention provides a kind of styrene ketone The preparation method of-maleic anhydride-butadiene-butenol antisludging agent and prepared antisludging agent, use Antisludging agent prepared by the method for the present invention not only scale inhibition performance is high, and biological degradation rate is high.
The technical solution adopted in the present invention is:
The preparation method of a kind of styrene ketone-maleic anhydride-butadiene-butenol antisludging agent, it is special Levying and be, the method includes: by styrene ketone, maleic anhydride, butadiene and butenol according to Mol ratio 1:(1-10): (3-16): after (4-20) mixing, add initiator, solvent and catalysis Agent carries out copolyreaction in the reactor, after obtaining yellow solid employing dimethyl fumarate dissolving Ether precipitates, is dried after filtering and pulverizes, obtaining styrene ketone-maleic anhydride-fourth two Alkene-butenol antisludging agent.
Preferably, described styrene ketone, maleic anhydride, butadiene and the mixing mole of butenol Ratio is 1:(2-7): (5-10): (8-16).
Preferably, described initiator is azobisisobutyronitrile and/or dibenzoyl peroxide, institute The mass ratio stating initiator and described styrene ketone is 1:(100-200).
Preferably, described solvent is benzene or butanone, described solvent and the quality of described styrene ketone Ratio is 100:(3-5).
Preferably, described catalyst is rare earth loaded diatomite catalyst, described rare earth be lanthanum, Cerium or praseodymium, the load capacity of described rare earth is 1-10 mass %.
Preferably, described reactor is tank reactor or paste state bed reactor.
Preferably, the condition of described copolyreaction is: temperature is 30-90 DEG C, and pressure is 7-10 MPa, the time is 15 minutes-5 hours.
Preferably, described dry temperature is 50-90 DEG C, and the described dry time is that 2-10 is little Time.
Preferably, the average particle of described styrene ketone-maleic anhydride-butadiene-butenol antisludging agent Footpath is 10-200 nanometer.
The present invention also provide for the styrene ketone prepared by a kind of preparation method provided by the present invention- Maleic anhydride-butadiene-butenol antisludging agent.
The invention have the benefit that
The preparation method of the present invention is simple, pollution-free, it is easy to industrialization;
Antisludging agent prepared by the inventive method, scale inhibition performance is high, is suitable for the water quality of high inorganic salt content;
Antisludging agent biological degradation rate prepared by the inventive method is high, and environment will not cause permanent shadow Ring, be suitable for sustainable development.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearer, below will be to the present invention Technical scheme be described in detail.Obviously, described embodiment is only the present invention one Section Example rather than whole embodiments.Based on the embodiment in the present invention, this area Other realities all that those of ordinary skill is obtained on the premise of not making creative work Execute mode, broadly fall into the scope that the present invention is protected.
The present invention provides the system of a kind of styrene ketone-maleic anhydride-butadiene-butenol antisludging agent Preparation Method, it is characterised in that the method includes: by styrene ketone, maleic anhydride, butadiene With butenol according to mol ratio 1:(1-10): (3-16): (4-20) mixing after add initiator, Solvent and catalyst carry out copolyreaction in the reactor, obtain yellow solid and use fumaric acid two Methyl esters precipitates after dissolving in ether, is dried after filtering and pulverizes, obtaining styrene ketone-horse Carry out acid anhydrides-butadiene-butenol antisludging agent;Preferably, described styrene ketone, maleic anhydride, The mixing mol ratio of butadiene and butenol is 1:(2-7): (5-10): (8-16).
According to the present invention, initiator is used for causing copolyreaction, is that those skilled in the art know , described initiator can be azobisisobutyronitrile and/or dibenzoyl peroxide, described in draw The mass ratio sending out agent and described styrene ketone can be 1:(100-200).
According to the present invention, solvent is those skilled in the art's numerical value, and described solvent can be benzene Or butanone, described solvent can be 100:(3-5 with the mass ratio of described styrene ketone).
According to the present invention, described catalyst can be rare earth loaded diatomite catalyst, described dilute Soil can be lanthanum, cerium or praseodymium, and the load capacity of described rare earth can be 1-10 mass %.
According to the present invention, reactor is well-known to those skilled in the art, and preferably high pressure is anti- Answer device, can be tank reactor or paste state bed reactor.
According to the present invention, the condition of described copolyreaction can be: temperature is 30-90 DEG C, pressure Power is 7-10 MPa, and the time is 15 minutes-5 hours, and described dry temperature can be 50-90 DEG C, the described dry time can be 2-10 hour.
According to the present invention, in order to make scale inhibition effect the best, described styrene ketone-maleic acid The average grain diameter of acid anhydride-butadiene-butenol antisludging agent can be 10-200 nanometer.
The present invention also provide for the styrene ketone prepared by a kind of preparation method provided by the present invention- Maleic anhydride-butadiene-butenol antisludging agent.
The present invention will be further illustrated by embodiment below, but the present invention the most therefore and Any way limited.
If no special instructions, instrument of the present invention and reagent are and are purchased, the business of different brands Product do not affect specifically used.
The embodiment of the present invention uses static method to measure the scale inhibition effect of antisludging agent, concrete grammar bag Include:
20 milligrams of antisludging agents are added in 1 liter of calcium sulphate soln containing 10000 mg/litre, It is stirred under 40 degrees Celsius 12 hours, after terminating, measures the concentration of calcium sulphate soln, resistance Calcium sulphate soln concentration X100% before calcium sulphate soln concentration/stirring before dirt rate=stirring.
The biological degradation rate computational methods of antisludging agent prepared by the embodiment of the present invention are:
Inoculation will be added containing the nutrient solution 500 milliliters of antisludging agent (concentration is 2O mg/litre) Thing 1.0 milliliters, under the room temperature environment of 20 DEG C, is placed on shaking table concussion, starts in experiment The COD measuring sample respectively on 7th day, calculates degradation rate.
Embodiment 1
By styrene ketone, maleic anhydride, butadiene and butenol according to mol ratio 1:1:3: (4-20) adding dibenzoyl peroxide, benzene and load capacity after mixing is 1 mass % praseodymium load Diatomite catalyst carries out copolyreaction, initiator and described styrene in paste state bed reactor The mass ratio of ketone is 1:100, and solvent is 100:5 with the mass ratio of described styrene ketone, altogether The condition of poly-reaction is: temperature is 90 DEG C, and pressure is 8 MPas, and the time is 3 hours, Dimethyl fumarate is used to precipitate in ether, after filtering at 60 DEG C after dissolving to yellow solid Under be dried 8 hours and pulverize, obtain styrene ketone-maleic anhydride that average grain diameter is 10 nanometers -butadiene-butenol antisludging agent 1, measures scale inhibition performance and degradation rate, scale inhibition performance by antisludging agent 1 It is 96.3%, degradation rate 89.3%.
Embodiment 2
By styrene ketone, maleic anhydride, butadiene and butenol according to mol ratio 1:9:16: Adding azobisisobutyronitrile, benzene and load capacity after 20 mixing is that 7 mass % lanthanum load diatomite are urged Agent carries out the mass ratio of copolyreaction, initiator and described styrene ketone in tank reactor For 1:150, solvent is 100:3 with the mass ratio of described styrene ketone, the bar of copolyreaction Part is: temperature is 40 DEG C, and pressure is 10 MPas, and the time is 1 hour, obtains yellow solid Use dimethyl fumarate to precipitate in ether after dissolving, at 90 DEG C, be dried 8 after filtering Hour and pulverize, obtain styrene ketone-maleic anhydride-butadiene that average grain diameter is 200 nanometers -butenol antisludging agent 2, measures scale inhibition performance and degradation rate by antisludging agent 2, and scale inhibition performance is 92.8%, Degradation rate 97.1%.
Embodiment 3
By styrene ketone, maleic anhydride, butadiene and butenol according to mol ratio 1:5:8: Azobisisobutyronitrile and dibenzoyl peroxide, the butanone that mass ratio is 1:1 is added after 12 mixing It is that to carry out copolymerization in tank reactor anti-for 5 mass % ceriums load diatomite catalyst with load capacity Should, initiator is 1:200 with the mass ratio of described styrene ketone, solvent and described styrene The mass ratio of ketone is 100:4, and the condition of copolyreaction is: temperature is 70 DEG C, and pressure is 9 MPa, the time is 15 minutes, obtains after yellow solid uses dimethyl fumarate to dissolve in second Precipitating in ether, be dried 2 hours after filtering and pulverize at 50 DEG C, obtaining average grain diameter is Styrene ketone-maleic anhydride-butadiene-butenol the antisludging agent 3 of 50 nanometers, surveys antisludging agent 3 Determining scale inhibition performance and degradation rate, scale inhibition performance is 98.8%, degradation rate 94.1%.
Comparative example 1
Being added without antisludging agent and measure scale inhibition performance, scale inhibition performance is 52.4%.
From embodiment, antisludging agent prepared by the inventive method not only scale inhibition performance is high, and Degradation rate is high.

Claims (10)

1. a preparation method for styrene ketone-maleic anhydride-butadiene-butenol antisludging agent, It is characterized in that, the method includes: by styrene ketone, maleic anhydride, butadiene and butenol According to mol ratio 1:(1-10): (3-16): (4-20) mixing after add initiator, solvent and Catalyst carries out copolyreaction in the reactor, obtains yellow solid and uses dimethyl fumarate molten After solution in ether precipitate, after filtering be dried and pulverize, obtain styrene ketone-maleic anhydride- Butadiene-butenol antisludging agent.
Styrene ketone-maleic anhydride-butadiene the most according to claim 1-butenol resistance Dirt agent preparation method, it is characterised in that described styrene ketone, maleic anhydride, butadiene and The mixing mol ratio of butenol is 1:(2-7): (5-10): (8-16).
Styrene ketone-maleic anhydride-butadiene the most according to claim 1-butenol resistance The preparation method of dirt agent, it is characterised in that described initiator is azobisisobutyronitrile and/or mistake Oxidation dibenzoyl, described initiator is 1:(100-200 with the mass ratio of described styrene ketone).
Styrene ketone-maleic anhydride-butadiene the most according to claim 1-butenol resistance The preparation method of dirt agent, it is characterised in that described solvent is benzene or butanone, described solvent and institute The mass ratio stating styrene ketone is 100:(3-5).
Styrene ketone-maleic anhydride-butadiene the most according to claim 1-butenol resistance The preparation method of dirt agent, it is characterised in that described catalyst is rare earth loaded diatomite catalyst, Described rare earth is lanthanum, cerium or praseodymium, and the load capacity of described rare earth is 1-10 mass %.
Styrene ketone-maleic anhydride-butadiene the most according to claim 1-butenol resistance Dirt agent preparation method, it is characterised in that described reactor be tank reactor or slurry bed system anti- Answer device.
Styrene ketone-maleic anhydride-butadiene the most according to claim 1-butenol resistance The preparation method of dirt agent, it is characterised in that the condition of described copolyreaction is: temperature is 30-90 DEG C, pressure is 7-10 MPa, and the time is 15 minutes-5 hours.
Styrene ketone-maleic anhydride-butadiene the most according to claim 1-butenol resistance The preparation method of dirt agent, it is characterised in that described dry temperature is 50-90 DEG C, described dry The dry time is 2-10 hour.
Styrene ketone-maleic anhydride-butadiene the most according to claim 1-butenol resistance The preparation method of dirt agent, it is characterised in that described styrene ketone-maleic anhydride-butadiene-butylene The average grain diameter of alcohol antisludging agent is 10-200 nanometer.
10. the styrene ketone prepared by preparation method described in any one in claim 1-9 -maleic anhydride-butadiene-butenol antisludging agent.
CN201610129742.3A 2016-03-08 2016-03-08 Styrene ketone-maleic anhydride-butadiene-butenol scale inhibitor and preparation method thereof Pending CN105753182A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103145256A (en) * 2013-03-18 2013-06-12 武汉理工大学 Preparation method and application of ternary high polymer copolymer scale inhibitor
CN103717627A (en) * 2011-07-22 2014-04-09 巴斯夫欧洲公司 Process for producing maleic acid-isoprenol copolymers
JP2015150484A (en) * 2014-02-13 2015-08-24 栗田工業株式会社 Scale removal method and scale remover for steam generating apparatus

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103717627A (en) * 2011-07-22 2014-04-09 巴斯夫欧洲公司 Process for producing maleic acid-isoprenol copolymers
CN103145256A (en) * 2013-03-18 2013-06-12 武汉理工大学 Preparation method and application of ternary high polymer copolymer scale inhibitor
JP2015150484A (en) * 2014-02-13 2015-08-24 栗田工業株式会社 Scale removal method and scale remover for steam generating apparatus

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
寇杰等: "《油气集输技术数据手册》", 31 July 2013, 中国石化出版社 *

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