CN100579637C - Scale inhibitor and preparation for reverse osmosis membrane - Google Patents
Scale inhibitor and preparation for reverse osmosis membrane Download PDFInfo
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- CN100579637C CN100579637C CN200710185389A CN200710185389A CN100579637C CN 100579637 C CN100579637 C CN 100579637C CN 200710185389 A CN200710185389 A CN 200710185389A CN 200710185389 A CN200710185389 A CN 200710185389A CN 100579637 C CN100579637 C CN 100579637C
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Abstract
The invention discloses a reverse osmosis membrane used corrosion and scale inhibitor as well as the preparation method thereof, and belongs to the liquid separation technology field. The invention is used for improving the inhibition effectiveness of the scale inhibitor and reducing the cost. The invention has the technical proposal that the corrosion and scale inhibitor is composed of a basic constituent and additives, the basic constituent is prepared from materials by the weight units as follows: hydroxyethylidene diphosphonic acid of 4 to 5, sodium polyacrylate of 5 to 6, hydrolyzed polymaleic anhydride of 5 to 6, and polyepoxysulfosuccinic acid of 3 to 4. The invention is a non-phosphate, non-nitrogenous and green environmental protection upscale multi-element scale and corrosion inhibitor, which has excellent scale inhibition and dispersion performance aiming at calcium carbonate, calcium sulfate, barium sulfate, calcium fluoride and silica scale in water, the scale inhibition effect exceeds the common organic phosphine scale inhibitor, and the scale inhibition rate reaches 85 percent. The components of the invention have very good synergistic effect, the product performance is stable, the cost is low, and the price is one third lower than that of the similar product in the current market.
Description
Technical field
The present invention relates to a kind of chemical products and preparation method thereof,, belong to the liquid separation technology field especially for the corrosion inhibiting and descaling agent of water treatment reverse osmosis membrane.
Background technology
Counter-infiltration is to utilize the membrane separation technique of pressure reduction for power, and it can remove impurity such as various ions, molecule, colloid, bacterium in the water, is generally acknowledge at present efficient, low consumption, free of contamination water technology.In recent years along with the development of membrane technology, counter-infiltration is applied in the water treatment more and more widely goes.In Reverse Osmosis Water Treatment Technology, it is the key factor that influences the counter-infiltration system operating efficiency and membrane lifetime is reduced that film pollutes film fouling in other words.Pollute the adverse effect of bringing for eliminating or alleviating film, improve the operating efficiency of counter-infiltration system, use antisludging agent to become a kind of requisite means undoubtedly.Antisludging agent is a kind of good counter-infiltration additive, and it can suppress the formation of dirt, prolongs the service life of reverse osmosis membrane.Present used antisludging agent has and costs an arm and a leg, contains the harmful substance that is unfavorable for environmental protection in the use cost height, antisludging agent, problem such as scale inhibition performance is on the low side.Therefore, developing low-cost, high efficiency, the reverse osmosis antisludging agent that is beneficial to environmental protection have very important realistic meaning.
Summary of the invention
Technical problem to be solved by this invention is to overcome the defective of prior art and provide that a kind of preparation cost is low, scale inhibition performance is high, the corrosion inhibiting and descaling agent that is used for reverse osmosis membrane of environmental protection, and the present invention also will provide the preparation method of this slowly-releasing antisludging agent.
The technical scheme that addresses the above problem is:
A kind of corrosion inhibiting and descaling agent that is used for reverse osmosis membrane, its special feature is, comprise basic composition thing and auxiliary agent in the formation, (component is weight portion to described basic composition thing described in the foreign language except that indicating especially by following unit of weight, concentration is W/W) material make: HEDP 4～5, Sodium Polyacrylate 5～6, HPMA 5～6, poly-epoxy succinic acid 3～4.
The above-mentioned corrosion inhibiting and descaling agent that is used for reverse osmosis membrane, described auxiliary agent is three kinds, wherein auxiliary agent 1 is a sodium hydrogensulfite, its addition be basic composition thing gross weight 0.6～1%, auxiliary agent 2 is chlorine dioxide, its addition is that 0.1-0.3%, the auxiliary agent 3 of basic composition thing gross weight is the phenylpropyl alcohol triazole, and its addition is the 0.1-0.3% of basic composition thing gross weight.
A kind of preparation method who is used for the corrosion inhibiting and descaling agent of reverse osmosis membrane, it comprises the steps:
A. prepare burden: take by weighing basic composition thing and auxiliary agent by said ratio;
B. be mixed: HEDP is added in the reactor stir, adding Sodium Polyacrylate stirs, add HPMA again and stir, drip poly-epoxy succinic acid again and stir, add auxiliary agent 1 sodium hydrogensulfite, auxiliary agent 2 chlorine dioxide, auxiliary agent 3 phenylpropyl alcohol triazoles then successively;
C. pack: after treating that auxiliary agent fully dissolves, filter and package.
The above-mentioned preparation method who is used for the reverse osmosis membrane corrosion inhibiting and descaling agent, described Sodium Polyacrylate prepares according to following steps: the unit meter takes by weighing deionized water 150～200 by weight, acrylic acid 150～200, adding reactor stirs, be lower than under 60 ℃ of temperature, add NaOH and make PAA, transferring PH is 7～9, stirs and squeezes into gravity tank after 10 minutes; The unit meter takes by weighing deionized water 120 by weight, sodium hydrogensulfite 5～8, and ammonium persulfate 7～9 is dissolved in sodium hydrogensulfite, ammonium persulfate and is mixed with initator in the deionized water, squeezes into the initator gravity tank; When reactor is warming up to 80 ℃ ± 2 ℃, two PAA and initators of being added dropwise to, PAA and initator drip by weight 10: 1 ratio, and polyase 13 hour after insulation half an hour, promptly gets Sodium Polyacrylate.
Above-mentioned corrosion inhibiting and descaling agent and the preparation method who is used for reverse osmosis membrane, described HPMA prepares according to following steps: unit takes by weighing deionized water 800～900 by weight, maleic anhydride 150～200, ferric trichloride 0.22～0.24, ammonium persulfate 20～25, deionized water, maleic anhydride are added reactor, add the catalyst ferric trichloride then, be warming up to 90～100 ℃ of dissolvings, drip initator, initator adds the dilution of equivalent deionized water by ammonium persulfate and is made into, polyase 13 hour, be incubated 3 hours.
Above-mentioned corrosion inhibiting and descaling agent and the preparation method who is used for reverse osmosis membrane, described poly-epoxy succinic acid prepares according to following steps: unit takes by weighing deionized water 250～280 by weight, maleic anhydride 300～315,48% NaOH 200～220, to mix in deionized water and the maleic anhydride adding reactor, be lower than under 60 ℃ of temperature, the NaOH salify of dropping 48%, be warming up to 45～65 ℃, add the catalyst sodium tungstate, drip hydrogen peroxide and 48%NaOH simultaneously, transfer pH value 7～9, wherein the sodium tungstate addition is 1～2 unit of weight, and hydrogen peroxide and 48%NaOH addition unit meter by weight are respectively 220～250 and 60～70, drips to finish to be warming up to 60～70 ℃, epoxidation 2～3 hours, continue to be warming up to more than 90 ℃, take by weighing initator calcium hydroxide 10～15 unit of weights, add initator calcium hydroxide in two batches, added once in per 10 minutes, one of each plus thirty stirs, and promptly obtains poly-epoxy succinic acid.
Product of the present invention is the polynary anti-incrustation corrosion inhibitor of a kind of without phosphorus, non-nitrogen " green " environment-friendly type.It has good scale inhibition and dispersion performance to the calcium carbonate in the water, calcium sulfate, barium sulfate, calcirm-fluoride and silicon dirt, and scale inhibition effect is better than organic phosphine class antisludging agent commonly used, and scale inhibition performance is higher than like product 10% up to 85%.Having certain corrosion inhibition simultaneously, is a kind of polynary antisludging agent.Product biodegradability of the present invention is good, with chlorine good intermiscibility is arranged, and is good with other medicament compatibility, is particularly useful for the cooling water system under high-alkali, high hard, the high pH value condition, can realize the high concentration multiple operation.This product preparation method adopts unique formula and production technology, has good cooperative effect between each component, and properties of product are stable, with low cost, and price is not as good as 1/3rd of existing market like product.Based on These characteristics, product of the present invention can be used for substituting existing similar products at home and abroad.
The specific embodiment
Product of the present invention is equipped with HEDP (HEDP) by preparation poly-epoxy succinic acid (PESA), synthetic Sodium Polyacrylate (PAAS), HPMA (HAMP), makes a kind of inhibition reverse osmosis antisludging agent through adding additive compound again.Adopt the antisludging agent of this method preparation, remarkable advantage such as have energy-saving and environmental protection, the scope of application is extensive, anticorrosion-antiscaling property good, stable performance, cost are low.Several embodiment below are provided:
Embodiment 1
The polyacrylic acid sodium polymerization: unit takes by weighing deionized water 150 by weight, and acrylic acid 170 adds reactor and stirs, and is being lower than under 60 ℃ of temperature, adds NaOH and makes PAA, and transferring PH is 7～9, stirs and squeezes into gravity tank after 10 minutes; Unit takes by weighing deionized water 120 by weight, sodium hydrogensulfite 5, and ammonium persulfate 7 is dissolved in sodium hydrogensulfite, ammonium persulfate and is mixed with initator in the deionized water, squeezes into the initator gravity tank; When reactor is warming up to 80 ℃ ± 2 ℃, two PAA and initators of being added dropwise to, PAA and initator drip by weight 10: 1 ratio, and polyase 13 hour after insulation half an hour, promptly gets Sodium Polyacrylate.
HPMA is synthetic: unit takes by weighing deionized water 800 by weight, maleic anhydride 150, ferric trichloride 0.22, ammonium persulfate 22 adds reactor with deionized water, maleic anhydride, add the catalyst ferric trichloride then, be warming up to 90～100 ℃ of dissolvings, drip initator, initator adds the dilution of equivalent deionized water by ammonium persulfate and is made into, polyase 13 hour, be incubated 3 hours.
The poly-epoxy succinic acid polymerization is as follows: unit takes by weighing deionized water 250 by weight, maleic anhydride 300, the NaOH 200 of 48% (w/w), to mix in deionized water and the maleic anhydride adding reactor, be lower than under 60 ℃ of temperature, dripping 48% NaOH salify, be warming up to 45 ℃, add the catalyst sodium tungstate, drip hydrogen peroxide and 48%NaOH simultaneously, transfer pH value 7～9, wherein the sodium tungstate addition by weight unit be 1, hydrogen peroxide and 48%NaOH addition unit by weight are respectively 220 and 60, drip to finish and to be warming up to 60 ℃, epoxidation 2～3 hours continues to be warming up to more than 90 ℃, unit takes by weighing initator calcium hydroxide 11 by weight, adds calcium hydroxide in two batches.Added once in per 10 minutes, one of each plus thirty stirs, and promptly obtains poly-epoxy succinic acid.
The preparation of corrosion inhibiting and descaling agent:
Unit takes by weighing basic composition thing HEDP 5, Sodium Polyacrylate 5, HPMA 6, poly-epoxy succinic acid 4 by weight.Take by weighing auxiliary agent 1 sodium hydrogensulfite according to 0.6% of basic composition thing gross weight, take by weighing auxiliary agent 2 chlorine dioxide, take by weighing auxiliary agent 3 phenylpropyl alcohol triazoles according to 0.3% of basic composition thing gross weight according to 0.1% of basic composition thing gross weight.HEDP added begin in the reactor to stir, adding Sodium Polyacrylate stirred 10 minutes, adding HPMA again stirred 10 minutes, dripping poly-epoxy succinic acid again stirs, add auxiliary agent 1 sodium hydrogensulfite, auxiliary agent 2 chlorine dioxide, auxiliary agent 3 phenylpropyl alcohol triazoles then successively, after treating that auxiliary agent fully dissolves, filter and package.
Embodiment 2
Sodium Polyacrylate is synthetic: unit takes by weighing deionized water 200 by weight, and acrylic acid 180 adds reactor and stirs, and is being lower than under 60 ℃ of temperature, adds NaOH and makes PAA, and transferring PH is 7～9, stirs and squeezes into gravity tank after 10 minutes; Unit takes by weighing deionized water 120 by weight, sodium hydrogensulfite 7, and ammonium persulfate 8 is dissolved in sodium hydrogensulfite, ammonium persulfate and is mixed with initator in the deionized water, squeezes into the initator gravity tank; When reactor is warming up to 80 ℃ ± 2 ℃, two PAA and initators of being added dropwise to, PAA and initator drip by weight 10: 1 ratio, and polyase 13 hour after insulation half an hour, promptly gets Sodium Polyacrylate.
HPMA is synthetic: unit takes by weighing deionized water 900 by weight, maleic anhydride 180, ferric trichloride 0.23, ammonium persulfate 20 adds reactor with deionized water, maleic anhydride, add the catalyst ferric trichloride then, be warming up to 90～100 ℃ of dissolvings, drip initator, initator adds the dilution of equivalent deionized water by ammonium persulfate and is made into, polyase 13 hour, be incubated 3 hours.
Poly-epoxy succinic acid is polymerization as follows: unit takes by weighing deionized water 280 by weight, maleic anhydride 315,48% NaOH210, to mix in deionized water and the maleic anhydride adding reactor, be lower than under 60 ℃ of temperature, dripping 48% NaOH salify, be warming up to 65 ℃, add the catalyst sodium tungstate, drip hydrogen peroxide and 48%NaOH simultaneously, transfer pH value 7～9, wherein the sodium tungstate addition by weight unit be 2, hydrogen peroxide and 48%NaOH addition unit by weight are respectively 250 and 70, drip to finish and to be warming up to 70 ℃, epoxidation 2～3 hours continues to be warming up to more than 90 ℃, unit takes by weighing initator calcium hydroxide 10 by weight, adds calcium hydroxide in two batches.Added once in per 10 minutes, one of each plus thirty stirs, and promptly obtains poly-epoxy succinic acid.
The preparation of corrosion inhibiting and descaling agent:
Unit takes by weighing basic composition thing HEDP 4, Sodium Polyacrylate 6, HPMA 5, poly-epoxy succinic acid 3 by weight.Take by weighing auxiliary agent 1 sodium hydrogensulfite according to 1% of basic composition thing gross weight, take by weighing auxiliary agent 2 chlorine dioxide, take by weighing auxiliary agent 3 phenylpropyl alcohol triazoles according to 0.2% of basic composition thing gross weight according to 0.2% of basic composition thing gross weight.HEDP added begin in the reactor to stir, adding Sodium Polyacrylate stirred 10 minutes, adding HPMA again stirred 10 minutes, dripping poly-epoxy succinic acid again stirs, add auxiliary agent 1 sodium hydrogensulfite, auxiliary agent 2 chlorine dioxide, auxiliary agent 3 phenylpropyl alcohol triazoles then successively, after treating that auxiliary agent fully dissolves, filter and package.
Embodiment 3
Sodium Polyacrylate is synthetic: unit takes by weighing deionized water 180 by weight, and acrylic acid 200 adds reactor and stirs, and is being lower than under 60 ℃ of temperature, adds NaOH and makes PAA, and transferring PH is 7～9, stirs and squeezes into gravity tank after 10 minutes; Unit takes by weighing deionized water 120 by weight, sodium hydrogensulfite 8, and ammonium persulfate 9 is dissolved in sodium hydrogensulfite, ammonium persulfate and is mixed with initator in the deionized water, squeezes into the initator gravity tank; When reactor is warming up to 80 ℃ ± 2 ℃, two PAA and initators of being added dropwise to, PAA and initator drip by weight 10: 1 ratio, and polyase 13 hour after insulation half an hour, promptly gets Sodium Polyacrylate.
HPMA is synthetic: unit takes by weighing deionized water 850 by weight, maleic anhydride 200, ferric trichloride 0.24, ammonium persulfate 25 adds reactor with deionized water, maleic anhydride, add the catalyst ferric trichloride then, be warming up to 90～100 ℃ of dissolvings, drip initator, initator adds the dilution of equivalent deionized water by ammonium persulfate and is made into, polyase 13 hour, be incubated 3 hours.
Poly-epoxy succinic acid is polymerization as follows: unit takes by weighing deionized water 260 by weight, maleic anhydride 305,48% NaOH220, to mix in deionized water and the maleic anhydride adding reactor, be lower than under 60 ℃ of temperature, dripping 48% NaOH salify, be warming up to 55 ℃, add the catalyst sodium tungstate, drip hydrogen peroxide and 48%NaOH simultaneously, transfer pH value 7～9, wherein the sodium tungstate addition by weight unit be 1.5, hydrogen peroxide and 48%NaOH addition unit by weight are respectively 230 and 68, drip to finish and to be warming up to 68 ℃, epoxidation 2～3 hours continues to be warming up to more than 90 ℃, unit takes by weighing initator calcium hydroxide 15 by weight, adds calcium hydroxide in two batches.Added once in per 10 minutes, one of each plus thirty stirs, and promptly obtains poly-epoxy succinic acid.
The preparation of corrosion inhibiting and descaling agent:
Unit takes by weighing basic composition thing HEDP 4.5, Sodium Polyacrylate 5, HPMA 5.5, poly-epoxy succinic acid 4 by weight.Take by weighing auxiliary agent 1 sodium hydrogensulfite according to 0.8% of basic composition thing gross weight, take by weighing auxiliary agent 2 chlorine dioxide, take by weighing auxiliary agent 3 phenylpropyl alcohol triazoles according to 0.1% of basic composition thing gross weight according to 0.3% of basic composition thing gross weight.HEDP added begin in the reactor to stir, adding Sodium Polyacrylate stirred 10 minutes, adding HPMA again stirred 10 minutes, dripping poly-epoxy succinic acid again stirs, add auxiliary agent 1 sodium hydrogensulfite, auxiliary agent 2 chlorine dioxide, auxiliary agent 3 phenylpropyl alcohol triazoles then successively, after treating that auxiliary agent fully dissolves, filter and package.
Claims (6)
1. corrosion inhibiting and descaling agent that is used for reverse osmosis membrane, it is characterized in that, comprise basic composition thing and auxiliary agent in the formation, described basic composition thing is made by the material of following unit of weight part: HEDP 4～5, Sodium Polyacrylate 5～6, HPMA 5～6, poly-epoxy succinic acid 3～4.
2. the corrosion inhibiting and descaling agent that is used for reverse osmosis membrane according to claim 1, it is characterized in that, described auxiliary agent is three kinds, wherein auxiliary agent 1 is a sodium hydrogensulfite, its addition be basic composition thing gross weight 0.6～1%, auxiliary agent 2 is chlorine dioxide, its addition is that 0.1-0.3%, the auxiliary agent 3 of basic composition thing gross weight is the phenylpropyl alcohol triazole, and its addition is the 0.1-0.3% of basic composition thing gross weight.
3. one kind prepares the preparation method who is used for the reverse osmosis membrane corrosion inhibiting and descaling agent as claimed in claim 1 or 2, it is characterized in that it comprises the steps:
A. prepare burden: take by weighing basic composition thing and auxiliary agent by proportioning;
B. be mixed: under stirring, add basic composition thing HEDP, Sodium Polyacrylate, HPMA, dropping poly-epoxy succinic acid successively to reactor, behind the mixing, add auxiliary agent sodium hydrogensulfite, chlorine dioxide, phenylpropyl alcohol triazole successively again;
C. pack: after treating that auxiliary agent fully dissolves, filter and package.
4. the preparation method who is used for the reverse osmosis membrane corrosion inhibiting and descaling agent according to claim 3, it is characterized in that, the polymerization as follows of described Sodium Polyacrylate: unit serving takes by weighing deionized water 150～200 by weight, acrylic acid 150～200, add reactor and stir, be lower than under 60 ℃ of temperature, add NaOH and make PAA, transferring PH is 7～9, stirs and squeezes into gravity tank after 10 minutes; Unit takes by weighing deionized water 120 by weight, sodium hydrogensulfite 5～8, and ammonium persulfate 7～9 is dissolved in sodium hydrogensulfite, ammonium persulfate and is mixed with initator in the deionized water, squeezes into the initator gravity tank; When reactor is warming up to 80 ℃ ± 2 ℃, two PAA and initators of being added dropwise to, PAA and initator drip by weight 10: 1 ratio, and polyase 13 hour after insulation half an hour, promptly gets Sodium Polyacrylate.
5. the preparation method who is used for the reverse osmosis membrane corrosion inhibiting and descaling agent according to claim 3, it is characterized in that, described HPMA prepares as follows: unit serving takes by weighing deionized water 800～900 by weight, maleic anhydride 150～200, ferric trichloride 0.22～0.24, ammonium persulfate 20～25, deionized water, maleic anhydride are added reactor, add the catalyst ferric trichloride then, be warming up to 90～100 ℃ of dissolvings, drip initator, initator adds the dilution of equivalent deionized water by ammonium persulfate and is made into, polyase 13 hour, be incubated 3 hours.
6. the preparation method who is used for the reverse osmosis membrane corrosion inhibiting and descaling agent according to claim 3, it is characterized in that, described poly-epoxy succinic acid prepares as follows: unit takes by weighing deionized water 250～280 by weight, maleic anhydride 300～315,48% NaOH200～220, to mix in deionized water and the maleic anhydride adding reactor, be lower than under 60 ℃ of temperature, dripping 48% NaOH salify, be warming up to 45～65 ℃, add the catalyst sodium tungstate, drip hydrogen peroxide and 48%NaOH simultaneously, transfer pH value 7～9, wherein the sodium tungstate addition by weight unit be 1～2, hydrogen peroxide and 48%NaOH addition unit by weight are respectively 220～250 and 60～70, drip to finish and to be warming up to 60～70 ℃, epoxidation 2～3 hours continues to be warming up to more than 90 ℃, unit takes by weighing initator calcium hydroxide 10～15 by weight, add initator calcium hydroxide in two batches, added once in per 10 minutes, one of each plus thirty, stir, promptly obtain poly-epoxy succinic acid.
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| CN200710185389A CN100579637C (en) | 2007-12-13 | 2007-12-13 | Scale inhibitor and preparation for reverse osmosis membrane |
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| CN200710185389A CN100579637C (en) | 2007-12-13 | 2007-12-13 | Scale inhibitor and preparation for reverse osmosis membrane |
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| CN100579637C true CN100579637C (en) | 2010-01-13 |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101580311B (en) * | 2009-06-24 | 2012-02-29 | 安徽省蓝天化工有限公司 | Polymaleic acid boiler scale-inhibition corrosion inhibitor |
| CN101967024B (en) * | 2010-06-04 | 2012-06-27 | 内蒙古天晨科技有限责任公司 | Phosphorus-free corrosion and scale inhibitor |
| CN101948189B (en) * | 2010-09-02 | 2012-05-23 | 蓝星环境工程有限公司 | Non-phosphorus reverse osmosis membrane scale inhibitor and preparation method thereof |
| CN102363113B (en) * | 2011-09-09 | 2013-10-23 | 贵阳时代沃顿科技有限公司 | Method for strengthening contamination resistance of reverse osmosis membrane |
| JP6146075B2 (en) * | 2013-03-22 | 2017-06-14 | 栗田工業株式会社 | Scale prevention method and scale inhibitor |
| CN104355419A (en) * | 2014-12-03 | 2015-02-18 | 天津天和环能科技有限公司 | Multifunctional scale and corrosion inhibitor and preparation method thereof |
| CN105753818B (en) * | 2014-12-17 | 2017-11-14 | 怀来县长城生物化学工程有限公司 | The method of synthesizing epoxy calcium succinate suspension and the method for production L (+) tartaric acid |
| CN104773846A (en) * | 2015-04-14 | 2015-07-15 | 宜昌大川科技有限公司 | Salt-manufacturing anti-deposition agent and method for preventing salt-manufacturing equipment from scale deposition |
| CN104923078A (en) * | 2015-06-10 | 2015-09-23 | 上海丰信环保科技有限公司 | Scale inhibitor for antibacterial reverse-osmosis membrane for printing and dyeing wastewater |
| CN106479467A (en) * | 2016-08-30 | 2017-03-08 | 陕西省石油化工研究设计院 | A kind of environment-friendly type is fluorinated calcium inhibitorses |
| CN106830377A (en) * | 2017-03-08 | 2017-06-13 | 陕西理工学院 | A kind of preparation method of antisludging agent |
| CN112023711A (en) * | 2019-06-04 | 2020-12-04 | 福州源洁环保科技有限公司 | RO reverse osmosis membrane treating agent and preparation method thereof |
| CN114656046B (en) * | 2022-04-29 | 2023-12-22 | 湖南诚通天岳环保科技有限公司 | Scale inhibitor for waste paper papermaking wastewater system and preparation method thereof |
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2007
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