CN108946967A - Environmentally friendly dirt dispersion agent and preparation method thereof - Google Patents
Environmentally friendly dirt dispersion agent and preparation method thereof Download PDFInfo
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- CN108946967A CN108946967A CN201810873074.4A CN201810873074A CN108946967A CN 108946967 A CN108946967 A CN 108946967A CN 201810873074 A CN201810873074 A CN 201810873074A CN 108946967 A CN108946967 A CN 108946967A
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- maleic anhydride
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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
- 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
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Abstract
The invention proposes a kind of environmentally friendly dirt dispersion agents and preparation method thereof, according to the number of parts by weight, including following raw material: 40~60 parts of maleic anhydride, 25~35 parts of itaconic acid, 25~35 parts of hydroxy-ethyl acrylate, 30~40 parts of cyclodextrin, 8~16 parts of initiator and 150~200 parts of water.Preparation method: 1) maleic anhydride aqueous solution is prepared；2) initiator solution is prepared；3) maleic anhydride aqueous solution is warming up to 60~100 DEG C, then itaconic acid, hydroxy-ethyl acrylate and remaining water is added, after mixing evenly, initiator solution is added dropwise, when 40~60wt% initiator solution has been added dropwise in maleic anhydride aqueous solution, cyclodextrin is added and is further continued for that remaining initiator solution is added dropwise, is stirred when being added dropwise, 2~3h of subsequent continuation of insurance temperature is added dropwise, is cooled to room temperature.Said preparation not only has very strong calcium scale-inhibiting properties, also has steady zinc and iron oxide dispersibility well.
Description
Technical field
The invention belongs to water-treatment technology fields, and in particular to a kind of environmentally friendly dirt dispersion agent and its preparation side
Method.
Background technique
In industrial recirculating cooling water system, due to water temperature raising, the evaporation of water, various inorganic ions and organic matter
The concentration of matter increases the hardness, basicity and pH value of recirculated water naturally, the alkaline earth metal cation contained in water such as Ca2+、Mg2+、
Ba2+With a small amount of other cations such as Fe2+、Fe3+、Cu2+、Al3+、Zn2+Deng meeting and the SO in water4 2-、CO3 2-、HCO3 -、OH-、
PO4 3-、SiO3 2-Equal anion generate slightly solubility inorganic salts such as Ca3(PO4)2、Ca(CO3)2、CaSO4、Mg(OH)2Deng, in pipeline and
Deposited on surface of heat exchanger reduces so as to cause heat exchanger heat transfer efficiency and causes underdeposit corrosion at dirt, wastes mass energy,
Reduce the service life of whole system.
In industrial circulating cooling water treatment process, the method control fouling and corrosion for adding chemical agent are mostly used greatly,
It can prevent scale and dirt from generating or the chemical agent of its deposition growing is inhibited generally all to be referred to as antisludging agent.Antisludging agent exists
Industrial common form mainly has corrosion inhibiter and two kinds of dispersing agent.
Corrosion inhibiter mainly has inorganic polymeric phosphate, organic multicomponent phosphoric acid, gluconic acid and tannic acid etc., at present recirculated water
Phosphorus line formulation is mostly used in system, more is organic multicomponent phosphonic acids, such as 1-hydroxy ethylidene-1,1-diphosphonic acid (HDPE), amino three
Methylenephosphonic acid (ATMP), ethylene diamine tetra methylene phosphonic acid (EDTMP) etc., since its molecular weight is low, functional group is less, to influence
Its performance；In addition contain a large amount of phosphorus in organic multicomponent phosphonic acids, the eutrophication of water proximate can be caused after discharge.
Dispersing agent be mainly in, low average molecular water-soluble polymer, including homopolymer and copolymer two major classes.Polymer
Have scale-inhibiting properties excellent as environmentally friendly dirt dispersion agent, dispersion performance is good, thermal stability insensitive to oxidant
Good, it is always the hot spot of water treatment field research that phosphorus content is low or not phosphorous equal many advantages.At present polymer from homopolymer by
Binary, ternary and multiple copolymer are gradually developed to, the various monomers with different function are largely introduced, and a uniqueness is formd
Field.The present common polymer of domestic contrast mainly has carboxylic acid quasi polymer, sulfonic acid quasi polymer, phosphorous quasi polymer
Deng, but document report is less at home for the copolymer of ethers containing alkene.
Chinese patent literature CN101805068A (application number 201010147936.9) discloses a kind of environmentally friendly resistance
Dirty dispersing agent and preparation method thereof, which is the copolymer of maleic anhydride and propenyl ether, described
Propenyl ether is acrylic polyoxyethylene ether；Initiator is added dropwise into the aqueous solution containing maleic anhydride, propenyl ether when preparation
Ammonium persulfate aqueous solution is added dropwise, and is stirred to react at 60 DEG C~90 DEG C 3~6 hours.The antisludging agent is bipolymer resistance
Dirty agent hinders calcium carbonate scale better performances, but does not embody other scale inhibition and dispersion performances, and application range is narrow.
Summary of the invention
The present invention proposes that a kind of environmentally friendly dirt dispersion agent, said preparation not only have very strong calcium scale-inhibiting properties, also
With good steady zinc and iron oxide dispersibility.
The technical scheme of the present invention is realized as follows:
A kind of environmentally friendly dirt dispersion agent, according to the number of parts by weight, including following raw material:
40~60 parts of maleic anhydride, 25~35 parts of itaconic acid, 25~35 parts of hydroxy-ethyl acrylate, 30~40 parts of cyclodextrin,
8~16 parts of initiator and 150~200 parts of water.
Preferably, the initiator is the mixture of ammonium persulfate and sodium hydrogensulfite.
Preferably, the mass ratio of the ammonium persulfate and the sodium hydrogensulfite is 2~4:1.
It is a further object to provide a kind of preparation methods of environmentally friendly dirt dispersion agent, including following step
It is rapid:
1) it is spare that maleic anhydride, itaconic acid, hydroxy-ethyl acrylate, cyclodextrin, initiator and water are weighed according to the proportion, first will
Stirring and dissolving after maleic anhydride is mixed with part water obtains maleic anhydride aqueous solution；
2) initiator is dissolved in small part water and initiator solution is prepared；
3) the maleic anhydride aqueous solution of step 1) is warming up to 60~100 DEG C, itaconic acid, hydroxy-ethyl acrylate is then added
With remaining water, after mixing evenly, a dropping step 2) initiator solution, when 40~60wt% initiator solution has dripped
When addition in maleic anhydride aqueous solution, stop that initiator solution is added dropwise, and it is water-soluble that cyclodextrin is added to maleic anhydride
After liquid is uniformly mixed, continue that remaining initiator solution is added dropwise, stir when being added dropwise, be added dropwise subsequent continuation of insurance warm 2~
3h is cooled to room temperature.
Beneficial effects of the present invention:
Cyclodextrin is the product that cyclodextrin transglucosylase (CGTase) acts on starch, is by six or more glucose
With α-Isosorbide-5-Nitrae-glycosidic bond connection member cyclic oligosaccharides, wherein most common, most study is alpha-cyclodextrin (α-
Cyclodextrin), beta-cyclodextrin (β-cyclodextrin), gamma-cyclodextrin (γ-cyclodextrin), respectively by six,
Seven and eight glucose molecules compositions, are relatively large and relatively flexible molecules.Through X-ray diffraction and nuclear magnetic resonance research,
Cyclodextrin molecular is proved into cone column or coniform garland, there are many rotatable key and hydroxyls, inside there is a cavity, apparent outer
Type is similar to the rubber stopper for connecing conduit.Cavity inside, which arranges, matches glycosyloxy bridge atom, the nonbonding electron of oxygen atom to the center of direction,
Make cavity inside that there is very high electron density, shows the property of part lewis base.It is surprisingly found by the inventors that ring is pasted
Essence is added in the initiation system of maleic anhydride, and the characteristic that one side has given full play to cyclodextrin itself makes it have in alkalinity
The performance for dispersing iron, zinc hydroxide and calcium phosphate in aqueous solution, on the other hand improves the scale-inhibiting properties of maleic anhydride itself.
The dosage of environmentally friendly dirt dispersion agent of the invention is 4~16mg/L, and dosage is less, under static state, temperature
In 90 DEG C, pH value 7 or so, scale-inhibiting properties can reach 90% or more, and dispersion performance can reach 85% or more.
Specific embodiment
Embodiment 1
A kind of environmentally friendly dirt dispersion agent, according to the number of parts by weight, including following raw material:
50 parts of maleic anhydride, 30 parts of itaconic acid, 29 parts of hydroxy-ethyl acrylate, 36 parts of cyclodextrin, 11 parts of initiator and water 170
Part.Initiator is the mixture of ammonium persulfate and sodium hydrogensulfite.The mass ratio of ammonium persulfate and the sodium hydrogensulfite is
3:1。
The preparation method of environmentally friendly dirt dispersion agent, comprising the following steps:
1) it is spare that maleic anhydride, itaconic acid, hydroxy-ethyl acrylate, cyclodextrin, initiator and water are weighed according to the proportion, first will
Stirring and dissolving after maleic anhydride is mixed with part water obtains maleic anhydride aqueous solution；
2) initiator is dissolved in small part water and initiator solution is prepared；
3) the maleic anhydride aqueous solution of step 1) is warming up to 80 DEG C, itaconic acid, hydroxy-ethyl acrylate is then added and remained
Remaining water, after mixing evenly, a dropping step 2) initiator solution, when 50wt% initiator solution has been added dropwise to Malaysia
When in acid anhydrides aqueous solution, stop that initiator solution is added dropwise, and cyclodextrin is added to the stirring of maleic anhydride aqueous solution and is mixed
After closing uniformly, continue that remaining initiator solution is added dropwise, is stirred when being added dropwise, subsequent continuation of insurance temperature 2h is added dropwise, is cooled to room
Temperature.
Embodiment 2
A kind of environmentally friendly dirt dispersion agent, according to the number of parts by weight, including following raw material:
40 parts of maleic anhydride, 25 parts of itaconic acid, 35 parts of hydroxy-ethyl acrylate, 30 parts of cyclodextrin, 8 parts of initiator and water 150
Part.Initiator is the mixture of ammonium persulfate and sodium hydrogensulfite.The mass ratio of ammonium persulfate and the sodium hydrogensulfite is
4:1。
The preparation method of environmentally friendly dirt dispersion agent, comprising the following steps:
1) it is spare that maleic anhydride, itaconic acid, hydroxy-ethyl acrylate, cyclodextrin, initiator and water are weighed according to the proportion, first will
Stirring and dissolving after maleic anhydride is mixed with part water obtains maleic anhydride aqueous solution；
2) initiator is dissolved in small part water and initiator solution is prepared；
3) the maleic anhydride aqueous solution of step 1) is warming up to 60 DEG C, itaconic acid, hydroxy-ethyl acrylate is then added and remained
Remaining water, after mixing evenly, a dropping step 2) initiator solution, when 40wt% initiator solution has been added dropwise to Malaysia
When in acid anhydrides aqueous solution, stop that initiator solution is added dropwise, and cyclodextrin is added to the stirring of maleic anhydride aqueous solution and is mixed
After closing uniformly, continue that remaining initiator solution is added dropwise, is stirred when being added dropwise, subsequent continuation of insurance temperature 3h is added dropwise, is cooled to room
Temperature.
Embodiment 3
A kind of environmentally friendly dirt dispersion agent, according to the number of parts by weight, including following raw material:
60 parts of maleic anhydride, 35 parts of itaconic acid, 25 parts of hydroxy-ethyl acrylate, 40 parts of cyclodextrin, 16 parts of initiator and water 200
Part.Initiator is the mixture of ammonium persulfate and sodium hydrogensulfite.The mass ratio of ammonium persulfate and the sodium hydrogensulfite is
2:1。
The preparation method of environmentally friendly dirt dispersion agent, comprising the following steps:
1) it is spare that maleic anhydride, itaconic acid, hydroxy-ethyl acrylate, cyclodextrin, initiator and water are weighed according to the proportion, first will
Stirring and dissolving after maleic anhydride is mixed with part water obtains maleic anhydride aqueous solution；
2) initiator is dissolved in small part water and initiator solution is prepared；
3) the maleic anhydride aqueous solution of step 1) is warming up to 100 DEG C, itaconic acid, hydroxy-ethyl acrylate is then added and remained
Remaining water, after mixing evenly, a dropping step 2) initiator solution, when 60wt% initiator solution has been added dropwise to Malaysia
When in acid anhydrides aqueous solution, stop that initiator solution is added dropwise, and cyclodextrin is added to the stirring of maleic anhydride aqueous solution and is mixed
After closing uniformly, continue that remaining initiator solution is added dropwise, is stirred when being added dropwise, subsequent continuation of insurance temperature 2h is added dropwise, is cooled to room
Temperature.
Test example
The static-state scale inhibition performance test of calcium carbonate is write " cooling referring to China Petrochemical Corporation of Sinopec
Moisture analysis and experimental method " " calcium phosphate deposition method " in (Sinopec publishing house, 1993) carry out, measuring temperature 90
℃。
The test method of the static-state scale inhibition performance of calcium sulfate are as follows: prepare 500ml with deionized water and contain certain density scale inhibition
Agent, 1800mgL-1Ca2+、4800mg·L-1SO4 2-Solution, adjust pH be 7, be subsequently placed in water bath with thermostatic control, in certain temperature
It is cooling after lower held for some time, it is filtered with 0.22 μm of millipore filter, with EDTA titration measuring Ca2+Ion concentration, together
When do blank assay, measuring temperature is 90 DEG C.
" the cooling moisture that the stability test of zinc ion is write referring to China Petrochemical Corporation of Sinopec
Analysis and experimental method " " deposition of zinc salt method " in (Sinopec publishing house, 1993) carry out, and measuring temperature is 90 DEG C.
The test of corrosion inhibition is referring to " National Standard of the People's Republic of China GB/T18175-2000, water treatment agent inhibition
The measurement of performance-rotary hanging plate method ", using progress corrosion inhibition experiment on RCC-II type rotary hanging plate corrosion tester, temperature
45 DEG C, revolving speed 75r/min of degree, not pre- film lacing film, experimental period 72 hours；Carbon steel test piece: 20# carbon steel, 50mm × 25mm ×
2mm.High-alkali, high hard water quality is selected in scale inhibition experiment, and water quality indicator is as shown in table 1.
Table 1
Note: total hardness, basicity, Ca2+With CaCO3Meter, mgL-1。
Performance test experimental result is shown in Table 2:
Table 2
Indicate: calcium carbonate scale inhibition experimental pharmacy concentration is 8mgL-1；Calcium sulfate scale inhibition experimental pharmacy concentration is 10mgL-1；Deposition of zinc salt experimental pharmacy concentration is 12mgL-1；Corrosion inhibition experimental pharmacy concentration is 16mgL-1。
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (4)
1. a kind of environmentally friendly dirt dispersion agent, which is characterized in that according to the number of parts by weight, including following raw material:
40~60 parts of maleic anhydride, 25~35 parts of hydroxy-ethyl acrylate, 30~40 parts of cyclodextrin, causes 25~35 parts of itaconic acid
8~16 parts of agent and 150~200 parts of water.
2. environmentally friendly dirt dispersion agent according to claim 1, which is characterized in that the initiator is ammonium persulfate
With the mixture of sodium hydrogensulfite.
3. environmentally friendly dirt dispersion agent according to claim 1, which is characterized in that the ammonium persulfate and the Asia
The mass ratio of sodium bisulfate is 2~4:1.
4. the preparation method of environmentally friendly dirt dispersion agent as described in claim 1, which is characterized in that including following step
It is rapid:
1) it is spare that maleic anhydride, itaconic acid, hydroxy-ethyl acrylate, cyclodextrin, initiator and water are weighed according to the proportion, first by Malaysia
Stirring and dissolving after acid anhydrides is mixed with part water obtains maleic anhydride aqueous solution；
2) initiator is dissolved in small part water and initiator solution is prepared；
3) the maleic anhydride aqueous solution of step 1) is warming up to 60~100 DEG C, itaconic acid, hydroxy-ethyl acrylate is then added and remained
Remaining water, after mixing evenly, a dropping step 2) initiator solution, when 40~60wt% initiator solution has been added dropwise to
When in maleic anhydride aqueous solution, stop that initiator solution is added dropwise, and cyclodextrin is added to maleic anhydride aqueous solution and is stirred
It mixes after mixing, continues that remaining initiator solution is added dropwise, stirred when being added dropwise, 2~3h of subsequent continuation of insurance temperature is added dropwise, it is cold
But to room temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810873074.4A CN108946967A (en) | 2018-08-02 | 2018-08-02 | Environmentally friendly dirt dispersion agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810873074.4A CN108946967A (en) | 2018-08-02 | 2018-08-02 | Environmentally friendly dirt dispersion agent and preparation method thereof |
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| Publication Number | Publication Date |
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| CN108946967A true CN108946967A (en) | 2018-12-07 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201810873074.4A Withdrawn CN108946967A (en) | 2018-08-02 | 2018-08-02 | Environmentally friendly dirt dispersion agent and preparation method thereof |
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2018
- 2018-08-02 CN CN201810873074.4A patent/CN108946967A/en not_active Withdrawn
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Application publication date: 20181207 |