CN105036364A - Method for preparing sulfo-type green scale inhibitor by using solid super acid catalyst - Google Patents
Method for preparing sulfo-type green scale inhibitor by using solid super acid catalyst Download PDFInfo
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- CN105036364A CN105036364A CN201510322754.3A CN201510322754A CN105036364A CN 105036364 A CN105036364 A CN 105036364A CN 201510322754 A CN201510322754 A CN 201510322754A CN 105036364 A CN105036364 A CN 105036364A
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- scale inhibitor
- sulfonic acid
- fundamental mode
- maleic anhydride
- green scale
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Abstract
The invention discloses a method for preparing a sulfo-type green scale inhibitor by using a solid super acid catalyst, which comprises the following steps: adding maleic anhydride and a catalyst into a three-neck flask provided with a thermometer, a condensation tube and a dropping funnel, heating until the maleic anhydride is molten, slowly and dropwisely adding 30% H2O2 while keeping the flow rate at 2-4 drops/minute, keeping at a certain constant temperature for some time to perform epoxy reaction, sequentially adding sodium alkyl sulfonate and an initiator, regulating the polymerization temperature, keeping the temperature constant for some time, and after the polymerization reaction finishes, obtaining a light yellow or reddish brown thick liquid which is the sulfo-type polymer. The sulfo-type green scale inhibitor is free of nitrogen, phosphorus and benzene ring groups in the molecular structure, is nontoxic and environment-friendly, and has favorable water solubility and scale inhibition and dispersion properties. The method lowers the cost, is suitable for large-scale production, and enhances the conversion rate.
Description
Technical field
The present invention relates to a kind of method preparing sulfonic acid fundamental mode green scale inhibitor, specifically a kind of method adopting solid superacid as catalyst to prepare sulfonic acid fundamental mode green scale inhibitor.
Background technology
In industrial water system, dirt is one of the main harm except material and facility corrosion, in order to avoid or slow down formation and the harm of incrustation scale, generally adopt and add Scale Inhibitors for Water in feedwater or recirculated cooling water.Mostly current domestic conventional water conditioner is phosphorous nitrogenous organic or inorganic compound, and the phosphorus that the whole nation produces for corrosion inhibiting and descaling agent according to statistics just has 100,000 t/a, and these phosphorous compounds as waste discharge, will cause potentially contaminated to environment.Along with the enhancing of people's environmental consciousness, the without phosphorus nitrogen discharged reality incorporating legislations of environmental protection in western countries of low-phosphorous nitrogen simultaneously, phosphorus line formulation has faced the destiny be eliminated.
Poly-epoxy succinic acid (PESA) is a kind of without phosphorus without nitrogen and the good water treatment agent having scale inhibitor dual-use function concurrently of biological degradability.Single due to PESA functional group, result in its performance single.For improving the scale inhibition and dispersion performance of PESA, people start research PESA being carried out to synthesis modification gradually, namely in synthetic polymer process, introduce the functional groups such as sulfonic group, carboxylic acid group, amido and hydroxyl by copolymerization or grafting method.At present in synthesis exploitation, from documents and materials both domestic and external be substantially all adopt same synthetic route, main is epoxidation catalyst with sodium wolframate, hydrogen peroxide is oxygenant, epoxidation reaction is carried out to maleic anhydride, then, under the effect of initiator calcium hydroxide, with containing monomer polymerization reaction take places such as Phenylsulfonic acid base class or nitrogenous AMPS, obtain containing phenyl ring or nitrogenous class sulfonic group Scale inhibitors.Wherein contain Phenylsulfonic acid base class Scale inhibitors on thermal stability, relatively poor; Meanwhile, be difficult to biological degradation in the environment containing phenyl ring class water conditioner, potential hazard is existed to environment; Nitrogenous class sulfonic group Scale inhibitors causes potentially contaminated problem to environment in addition.
Summary of the invention
The object of the present invention is to provide a kind of method adopting solid superacid as catalyst to prepare sulfonic acid fundamental mode green scale inhibitor, to solve the problem proposed in above-mentioned background technology.
For achieving the above object, the invention provides following technical scheme:
A kind of method adopting solid superacid as catalyst to prepare sulfonic acid fundamental mode green scale inhibitor, comprise the following steps: in the there-necked flask that thermometer, prolong and dropping funnel are housed, add maleic anhydride and catalyzer, be heated to maleic anhydride melt, more slowly drip 30%H
2o
2coutroi velocity is at 2drop/min ~ 4drop/min, keep certain temperature, constant temperature certain hour, after epoxy reaction, add sodium allyl sulfonate and initiator successively, regulate polymerization temperature, constant temperature for some time, polyreaction terminates, obtain light yellow or reddish-brown thick liquid, obtain sulfonic acid fundamental mode polymkeric substance.
As the further scheme of the present invention: described catalyzer is SO
4 2-/ M
xo
yseries solid super-strong acid, is specially: SO
4 2-/ ZnO, SO
4 2-/ TiO
2, SO
4 2-/ Al
2o
3, SO
4 2-/ Fe
2o
3, SO
4 2-/ ZrO
2, SO
4 2-/ TiO
2-SiO
2, SO
4 2-/ SiO
2-Al
2o
3, SO
4 2-/ ZrO
2-TiO
2.
As the present invention's further scheme: the amount of substance ratio of described catalyzer and maleic anhydride is 0.0025 ~ 0.03.
As the present invention's further scheme: the amount of substance ratio of described maleic anhydride and sodium allyl sulfonate is 0.33 ~ 4.
As the present invention's further scheme: described epoxy reactive temperature is 60 DEG C ~ 100 DEG C, and the time is 80min ~ 180min.
As the present invention's further scheme: described 30%H
2o
2dosage is 0.5 ~ 3 with the amount of substance ratio of maleic anhydride.
As the present invention's further scheme: described initiator is NaOH or ammonium persulphate, described initiator dosage is 0.05 ~ 2.5 with the amount of substance ratio of maleic anhydride.
As the present invention's further scheme: the temperature of described polyreaction is 80 DEG C ~ 120 DEG C, and the time is 60min ~ 240min.
Compared with prior art, the invention has the beneficial effects as follows: not containing nitrogen, phosphorus and phenyl ring class group in (1) sulfonic acid fundamental mode green scale inhibitor molecular structure, nontoxic, belong to environmentally friendly and there is good water-soluble and scale inhibition and dispersion; (2) avoiding the expensive sodium wolframate of use is catalyzer, have employed homemade SO
4 2-/ M
xo
yit is catalyzer that series solid super-strong acid substitutes sodium wolframate, and carries out " one kettle way " catalysis preparation; In synthetic reaction process, do not need the intermediate steps such as separation, purification, be applicable to large-scale production; (3) in melting process without water solvent, stopped maleic anhydride hydrolysis, thus improve transformation efficiency.
Accompanying drawing explanation
Fig. 1 is the structural representation of sulfonic acid fundamental mode green scale inhibitor.
Fig. 2 adopts solid superacid as catalyst to prepare sulfonic acid fundamental mode green scale inhibitor functional group infrared spectrum characterization figure in the method for sulfonic acid fundamental mode green scale inhibitor.
Fig. 3 adopts solid superacid as catalyst to prepare sulfonic acid fundamental mode green scale inhibitor electron-microscope scanning figure in the method for sulfonic acid fundamental mode green scale inhibitor.
Fig. 4 adopts solid superacid as catalyst to prepare sulfonic acid fundamental mode green scale inhibitor thermostability figure in the method for sulfonic acid fundamental mode green scale inhibitor.
Fig. 5 is the scale inhibition effect figure adopting solid superacid as catalyst to prepare the different dosages of sulfonic acid fundamental mode green scale inhibitor in the method for sulfonic acid fundamental mode green scale inhibitor.
Fig. 6 adopts solid superacid as catalyst to prepare the CaCO not adding Scale inhibitors in the method for sulfonic acid fundamental mode green scale inhibitor
3dirt electron-microscope scanning figure.
Fig. 7 adopts solid superacid as catalyst to prepare the CaCO adding Scale inhibitors in the method for sulfonic acid fundamental mode green scale inhibitor
3dirt electron-microscope scanning figure.
Fig. 8 adopts solid superacid as catalyst to prepare the Ca not adding Scale inhibitors in the method for sulfonic acid fundamental mode green scale inhibitor
3(PO
4) 2 dirty electron-microscope scanning figure.
Fig. 9 adopts solid superacid as catalyst to prepare the Ca adding Scale inhibitors in the method for sulfonic acid fundamental mode green scale inhibitor
3(PO
4)
2dirt electron-microscope scanning figure.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment one
To in the there-necked flask that thermometer, prolong and dropping funnel are housed, add the 20mol%SO of 0.05mol maleic anhydride and 0.0014mol
4 2-/ M
xo
yseries solid super-strong acid, is heated to maleic anhydride melt, more slowly drips the 30%H of 10ml
2o
2, coutroi velocity is 4drop/min, keeps 80 DEG C of temperature, after reaction 180min, add 0.1mol sodium allyl sulfonate and 0.005molNaOH successively, regulate polymerization temperature 120 DEG C, polyreaction 120min, after reaction terminates, obtain light yellow or brown viscous liquid, obtain sulfonic acid fundamental mode polymkeric substance.
Following instance is all with SO
4 2-/ ZnO solid super-strong acid is that sulfonic acid fundamental mode polymkeric substance is prepared in example catalysis.
Embodiment two
To in the there-necked flask that thermometer, prolong and dropping funnel are housed, add the 20mol%SO of 0.05mol maleic anhydride and 0.005mol
4 2-/ ZnO solid super-strong acid, is heated to maleic anhydride melt, more slowly drips the 30%H of 10ml
2o
2, coutroi velocity is 4drop/min, keeps 80 DEG C of temperature, after reaction 180min, add the NaOH of 0.1mol sodium allyl sulfonate and 0.2g, 0.005mol successively, regulate polymerization temperature 120 DEG C, polyreaction 120min, after reaction terminates, obtain yellow viscous liquid, obtain sulfonic acid fundamental mode polymkeric substance.The calcium carbonate and the calcium phosphate average efficiency that measure product are respectively 88.33% and 92.40%.
Embodiment three
To in the there-necked flask that thermometer, prolong and dropping funnel are housed, add the 20mol%SO of 0.2mol maleic anhydride and 0.003mol
4 2-/ ZnO solid super-strong acid, is heated to maleic anhydride melt, more slowly drips the 30%H of 7.5ml
2o
2, coutroi velocity is 4drop/min, keeps 80 DEG C of temperature, after reaction 120min, add 0.1mol sodium allyl sulfonate and 0.005molNaOH successively, regulate polymerization temperature 120 DEG C, polyreaction 90min, after reaction terminates, obtain pale yellow viscous liquid, obtain sulfonic acid fundamental mode polymkeric substance.The calcium carbonate and the calcium phosphate average efficiency that measure product are respectively 86.06% and 94.00%.
Embodiment four
To in the there-necked flask that thermometer, prolong and dropping funnel are housed, add the 20mol%SO of 0.05mol maleic anhydride and 0.005mol
4 2-/ ZnO solid super-strong acid, is heated to maleic anhydride melt, more slowly drips the 30%H of 9ml
2o
2, coutroi velocity is 2drop/min, keeps 100 DEG C of temperature, after reaction 120min, add 0.2mol sodium allyl sulfonate and 0.015molNaOH successively, regulate polymerization temperature 110 DEG C, polyreaction 120min, after reaction terminates, obtain reddish-brown thick liquid, obtain sulfonic acid fundamental mode polymkeric substance.The calcium carbonate and the calcium phosphate average efficiency that measure product are respectively 92.31% and 93.91%.
Embodiment five
To in the there-necked flask that thermometer, prolong and dropping funnel are housed, add the 20mol%SO of 0.05mol maleic anhydride and 0.0025mol
4 2-/ ZnO solid super-strong acid, is heated to maleic anhydride melt, more slowly drips the 30%H of 7.5ml
2o
2, coutroi velocity is 2drop/min, keeps 90 DEG C of temperature, after reaction 120min, add 0.15mol sodium allyl sulfonate and 0.015mol ammonium persulphate successively, regulate polymerization temperature 80 DEG C, polyreaction 120min, after reaction terminates, obtain yellow viscous liquid, obtain sulfonic acid fundamental mode polymkeric substance.The calcium carbonate and the calcium phosphate average efficiency that measure product are respectively 91.01% and 98.00%.
Mensuration-calcium phosphate deposition method according to " mensuration-tosca method of water conditioner scale-inhibiting properties " (GB/T16632-2008) and water conditioner scale-inhibiting properties " Scale inhibitors of above-mentioned gained carries out scale-inhibiting properties test by (GB/T22626-2008) method.Sulfonic acid fundamental mode green scale inhibitor of preparing prepared by the present invention has good calcium carbonate and the scale-inhibiting properties of calcium phosphate, especially better to the scale inhibition effect of calcium phosphate, average scale inhibition performance respectively in 71.35% ~ 98.87% and 77.38% ~ 99.8% scope, different SO
4 2-/ M
xo
ysolid superacid as catalyst prepares the calcium carbonate of products obtained therefrom and calcium phosphate average efficiency is shown in Table 1.
The different SO of table 1
4 2-/ M
xo
ysolid superacid as catalyst prepares the scale-inhibiting properties cartogram of sulfonic acid fundamental mode green scale inhibitor
Compare for nMA:nSAS:ncatalyst:nH with the amount of substance of other materials at the benchmark being 0.05mol with maleic anhydride consumption, maleic anhydride
2o
2: nNaOH=1:0.5:0.005:2:0.3, the H of 30%
2o
2flow rate control 4drop/min, temperature 80 DEG C of cyclization 120min, under constant temperature 120 DEG C of polyreaction 120min conditions, with SO
4 2-it is example that/ZnO solid superacid as catalyst prepares sulfonic acid fundamental mode polymkeric substance, investigate the scale inhibition efficiency of the sulfonic acid fundamental mode polymkeric substance of different concns, when sulfonic acid fundamental mode polymkeric substance dosage is 2mg/L, 4mg/L, 6mg/L, 8mg/L, 10mg/L and 12mg/L, the scale inhibition efficiency of calcium carbonate and calcium phosphate is respectively in 65.52% ~ 91.1% and 71.25% ~ 99.21% scope, and the scale inhibition efficiency ratio calcium carbonate of calcium phosphate is effective.
As Fig. 6-9, apply the present invention to calcium carbonate and the surface analysis of calcium phosphate crystalline form, can be found out by the electron-microscope scanning figure of Fig. 6-9, the crystal that the blank test sample that Fig. 6 and Fig. 8 does not add Scale inhibitors is separated out has regular cube structure, queueing discipline, shape are regular, tight, easy formation hard scale, the crystalline form that Fig. 7 and Fig. 9 separates out after adding sulfonic acid fundamental mode green scale inhibitor MA/SAS there occurs change, it is no longer regular form, lattice there occurs obvious distortion, become irregular, by cube structure englobement structure, cotton-shaped, the soft heap incrustation sample not having corner angle.
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned one exemplary embodiment, and when not deviating from spirit of the present invention or essential characteristic, the present invention can be realized in other specific forms.Therefore, no matter from which point, all should embodiment be regarded as exemplary, and be nonrestrictive, scope of the present invention is limited by claims instead of above-mentioned explanation, and all changes be therefore intended in the implication of the equivalency by dropping on claim and scope are included in the present invention.Any Reference numeral in claim should be considered as the claim involved by limiting.
In addition, be to be understood that, although this specification sheets is described according to embodiment, but not each embodiment only comprises an independently technical scheme, this narrating mode of specification sheets is only for clarity sake, those skilled in the art should by specification sheets integrally, and the technical scheme in each embodiment also through appropriately combined, can form other embodiments that it will be appreciated by those skilled in the art that.
Claims (8)
1. the method adopting solid superacid as catalyst to prepare sulfonic acid fundamental mode green scale inhibitor, it is characterized in that, comprise the following steps: in the there-necked flask that thermometer, prolong and dropping funnel are housed, add maleic anhydride and catalyzer, be heated to maleic anhydride melt, more slowly drip 30%H
2o
2coutroi velocity is at 2drop/min ~ 4drop/min, keep certain temperature, constant temperature certain hour, after epoxy reaction, add sodium allyl sulfonate and initiator successively, regulate polymerization temperature, constant temperature for some time, polyreaction terminates, obtain light yellow or reddish-brown thick liquid, obtain sulfonic acid fundamental mode polymkeric substance.
2. employing solid superacid as catalyst according to claim 1 prepares the method for sulfonic acid fundamental mode green scale inhibitor, it is characterized in that, described catalyzer is SO
4 2-/ M
xo
yseries solid super-strong acid, is specially: SO
4 2-/ ZnO, SO
4 2-/ TiO
2, SO
4 2-/ Al
2o
3, SO
4 2-/ Fe
2o
3, SO
4 2-/ ZrO
2, SO
4 2-/ TiO
2-SiO
2, SO
4 2-/ SiO
2-Al
2o
3, SO
4 2-/ ZrO
2-TiO
2.
3. employing solid superacid as catalyst according to claim 1 prepares the method for sulfonic acid fundamental mode green scale inhibitor, it is characterized in that, the amount of substance ratio of described catalyzer and maleic anhydride is 0.0025 ~ 0.03.
4. employing solid superacid as catalyst according to claim 1 prepares the method for sulfonic acid fundamental mode green scale inhibitor, it is characterized in that, the amount of substance ratio of described maleic anhydride and sodium allyl sulfonate is 0.33 ~ 4.
5. employing solid superacid as catalyst according to claim 1 prepares the method for sulfonic acid fundamental mode green scale inhibitor, it is characterized in that, described epoxy reactive temperature is 60 DEG C ~ 100 DEG C, and the time is 80min ~ 180min.
6. employing solid superacid as catalyst according to claim 1 prepares the method for sulfonic acid fundamental mode green scale inhibitor, it is characterized in that, described 30%H
2o
2dosage is 0.5 ~ 3 with the amount of substance ratio of maleic anhydride.
7. employing solid superacid as catalyst according to claim 1 prepares the method for sulfonic acid fundamental mode green scale inhibitor, it is characterized in that, described initiator is NaOH or ammonium persulphate, and described initiator dosage is 0.05 ~ 2.5 with the amount of substance ratio of maleic anhydride.
8. employing solid superacid as catalyst according to claim 1 prepares the method for sulfonic acid fundamental mode green scale inhibitor, it is characterized in that, the temperature of described polyreaction is 80 DEG C ~ 120 DEG C, and the time is 60min-240min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105776264A (en) * | 2016-02-06 | 2016-07-20 | 湖南诺兰蒂尔环保科技有限公司 | Scale inhibitor used in aluminum oxide production process |
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| JP2003192784A (en) * | 2001-10-18 | 2003-07-09 | Mitsui Takeda Chemicals Inc | Water-soluble polymer having biodegradability, its manufacturing method and its use |
| CN102616946A (en) * | 2011-06-23 | 2012-08-01 | 陕西省石油化工研究设计院 | Biodegradable corrosion and scale inhibitor epoxy succinic acid copolymer and its preparation method |
| CN103265124A (en) * | 2013-06-08 | 2013-08-28 | 成都润兴消毒药业有限公司 | Corrosion and scale inhibitor and preparation method thereof |
| CN103449616A (en) * | 2013-09-03 | 2013-12-18 | 山东天庆科技发展有限公司 | Biodegradable non-phosphorus scale inhibition dispersion agent and preparation method thereof |
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2015
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030073586A1 (en) * | 2001-10-03 | 2003-04-17 | Martin Crossman | Scale control composition for high scaling environments |
| JP2003192784A (en) * | 2001-10-18 | 2003-07-09 | Mitsui Takeda Chemicals Inc | Water-soluble polymer having biodegradability, its manufacturing method and its use |
| CN102616946A (en) * | 2011-06-23 | 2012-08-01 | 陕西省石油化工研究设计院 | Biodegradable corrosion and scale inhibitor epoxy succinic acid copolymer and its preparation method |
| CN103265124A (en) * | 2013-06-08 | 2013-08-28 | 成都润兴消毒药业有限公司 | Corrosion and scale inhibitor and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105776264A (en) * | 2016-02-06 | 2016-07-20 | 湖南诺兰蒂尔环保科技有限公司 | Scale inhibitor used in aluminum oxide production process |
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Effective date of registration: 20200709 Address after: 301700 Tianjin city Wuqing district town Huacheng Road No. 169, Cao. Patentee after: TIANJIN KUNPENG CHEMICAL TECHNOLOGY Co.,Ltd. Address before: 561011 Guizhou province Tongren area water Bijiang District of Tongren City Road No. 103 Patentee before: TONGREN University |