CN102358772A - Preparation method of phosphorus-free green environment-friendly scale inhibitor - Google Patents
Preparation method of phosphorus-free green environment-friendly scale inhibitor Download PDFInfo
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- CN102358772A CN102358772A CN2011102761889A CN201110276188A CN102358772A CN 102358772 A CN102358772 A CN 102358772A CN 2011102761889 A CN2011102761889 A CN 2011102761889A CN 201110276188 A CN201110276188 A CN 201110276188A CN 102358772 A CN102358772 A CN 102358772A
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Abstract
The invention discloses a preparation method of a phosphorus-free green environment-friendly scale inhibitor. The scale inhibitor is characterized by being a quarternary polymerization one and comprising components by weight of 25-40 parts of acomitic acid, 8-20 parts of acrylic acid, 12-18 parts of maleic anhydride, 6-12 parts of sodium alkyl sulfonate, 3-7 parts o fammonium persulfate and 130-220 parts of water. The invention also discloses a preparation method of the phosphorus-free green environment-friendly scale inhibitor. The scale inhibitor prepared by the invention has excellent scale inhibiting effects on scales of calcium carbonate, calcium phosphate and barium sulfate, and characteristics of rust inhibition, high temperature resistance, stable molecular weight and on phosphorus. The whole production process has no ''three wastes (waste gas, waste water and industrial residue)'' discharge. The product of the invention can be used for treating industrial circulating water and oil field water with a simple technology, and has small usage amount, low costs, good effect and good economic benefits and wide social benefits.
Description
Technical field
The invention belongs to chemical technology field, relate to a kind of preparation method of new polymers corrosion inhibiting and descaling agent, this Scale inhibitors is a kind of without phosphorus low molecule multipolymer, belongs to the environment-friendly Scale inhibitors.
Background technology
Along with the rapid increase of industrial mass-producing and population, water resources serious lack.Because cooling water amount accounts for 60～70% of process water, so it is particularly important rationally to practice thrift water coolant.The main method of practicing thrift water coolant is to improve cooling water circulation utilization ratio, strengthens the cycles of concentration of water coolant, but can bring serious corrosion and scale problems to cooling water system again like this, also Scale inhibitors is had higher requirement simultaneously.
Scale inhibitors is a kind of as water conditioner; Be widely used in the recirculating cooling water system of industries such as oil, chemical industry, electric power, papermaking, metallurgy, pharmacy; Since the sixties in 20th century; Water conditioner constantly develops, how with natural polymer xylogen, sodium phytate etc. as dirt dispersion agent, scale inhibition effect is not ideal enough.Succeeding in developing of ROHM at the beginning of the seventies (PAA) and polymaleic acid (PMA) makes Scale inhibitors handle the water coolant technology and makes a breakthrough, and driven a series of exploitation and uses that contain binary, ternary even the tetrapolymer of multiple group.At present; It is that 200410066828.3 " a kind of corrosion inhibiting and descaling agents that are used for industrial cooling circulating water system ", application number are 200610137772.5 " a kind of Scale inhibitors and in the application of water treatment ", application number are 200710051679.7 " preparing methods of highly effective maleic anhydride series polymer antisludging agent ", application number are that 200710022984.3 " a kind of non-phosphate environment-friendly type inhibition anti-sludging agents and preparation method thereof ", application number are that 2007101339925.5 " allyloxy polyether class Scale inhibitors and preparation method " application number is that 200710177189.1 " a kind of corrosion inhibition anti-sludging agent for boiler heating network ", application number are that 200810055017.1 " a kind of corrosion inhibiting and descaling agents of industrial circulating cooling water ", application number are 200810123729.2 " a kind of quadripolymer type corrosion inhibiting and descaling agents and preparation method thereof " or the like that Chinese patent discloses application number, and above-mentioned patented technology all adopts copolymerization.In recent years; The enhancing of Along with people's environmental consciousness; Synthesizing of biodegradable novel Scale inhibitors receives the concern in the world gradually; Many environmentally friendly Scale inhibitorss constantly come out; Wherein study more have SAP 73, poly-epoxy succinic acid; At present, it is that 02111415.3 " preparation method of polyasparagic acid as environment protecting scale inhibitor " application number is that 200410015875.5 " preparing methods of biodegradable corrosion inhibiting and descaling agent SAP 73 ", application number are that 200610012918.3 " a kind of aspartate copolymers and preparation method thereof ", application number are 200710173243.5 " being used as the preparation method of the glycocoll/aspartic acid multipolymer of green scale inhibitor " etc. that Chinese patent discloses application number, and the scale inhibition effect of aspartic acid class Scale inhibitors is fine; But price comparison is expensive, and a lot of enterprises do not use in order to reduce production costs.Comrades such as Zhang Yanhe have studied " research of the synthetic and performance of equisetic acid-PEMULEN TR2 " Treatment of Industrial Water; 2005,25 (2): 48～49, when add-on is 15mg/L; Scale inhibition performance reaches 65.71%; After this multipolymer and HEDP, PBTCA are compound, collaborative scale inhibition effect is arranged, its scale inhibition performance is respectively 76.80% and 83.91%.Because the complicacy and the polytropy of industrial cooling circulating water water quality; Compounded technology can not satisfy the requirement of Treatment of Industrial Water far away; Must use the multiple aggregation technology that more monomers that contain the different activities group are bonded in the polymer molecule more, give the performance of the more excellences of upgrading of water conditioner more.The present invention through experiment repeatedly, adopts the water law polymerization technique successfully to develop to use in the suitable Complex Water Environment after investigation domestic and international aggretion type water conditioner newest research results and experience, contain-COOH ,-SO
3H ,-the multiple aggregation type Scale inhibitors of OH isoreactivity group, excellent performance.
Summary of the invention
The compound method that the purpose of this invention is to provide a kind of without phosphorus, degradable, little, the pollution-free quaternary Scale inhibitors of consumption.
The object of the invention can reach through following measure:
A kind of Scale inhibitors is made up of equisetic acid, vinylformic acid, maleic anhydride, sodium allyl sulfonate, ammonium persulphate and water.The mass ratio of each component is preferably: equisetic acid 25～40, vinylformic acid 8～20, maleic anhydride 12～18, sodium allyl sulfonate 6～12, ammonium persulphate 3～7, water 130～220.
A kind of preparation method of phosphorus-free green environment protecting scale inhibitor comprises the steps:
(1) with maleic anhydride be dissolved in account for water inventory 35～50% between, under 50～60 ℃, make its abundant hydrolysis, be chilled to room temperature maleic anhydride solution by volume again: vinylformic acid is 1: 0.5～0.7 wiring solution-forming (I);
(2) with sodium allyl sulfonate and ammonium persulphate by mass ratio be example be dissolved in account for water inventory 35～50% between, wiring solution-forming (II);
(3) equisetic acid is dissolved in the remainder water, temperature is raised to 50～60 ℃, under agitation drips solution (I) (dripping speed control dropwises in 30min); Dropwise the back at 50～60 ℃ of following isothermal reaction 30min, temperature is elevated to 75～85 ℃ then, drips solution (II) (dripping speed control dropwises in 30min) again; All dropwise 75～85 ℃ of isothermal reactions 3～4 hours; Stopped reaction, about 50 ℃ in product Dropwise 5 0%NaOH solution, pH is transferred to weakly alkaline; Obtain a kind of reddish-brown transparent liquid, i.e. quaternary phosphorus-free green environment protecting scale inhibitor.
The Scale inhibitors of the present invention's preparation can be widely used in the recirculating cooling water system of industries such as oil, chemical industry, electric power, papermaking, metallurgy, pharmacy, suppresses cooling water scaling.
The following advantage of tool of the present invention: (1) dosage is few, cost is low, the scale inhibition ability is strong, good product quality, and the quality guaranteed period is more than 1 year; (2) without phosphorus, Heat stability is good, product is biodegradable; (3) the synthetic condition of crossing range request is controlled easily, and energy consumption is low, and is simple to operate, do not have " three wastes " discharging in the whole process of production, belongs to process for cleanly preparing.
Embodiment
Embodiment 1
(1) gets the 14g maleic anhydride and place few cup, be dissolved in the 20mL water, be heated to and make its abundant hydrolysis under 50 ℃, be chilled to room temperature, add 15mL vinylformic acid wiring solution-forming (I);
(2) get 10g sodium allyl sulfonate and 5g ammonium persulphate and be dissolved in the 20mL water, wiring solution-forming (II);
(3) get the 35g equisetic acid and be dissolved in the 60mL water, temperature is raised to 50 ℃, under agitation drips solution (I); Dropwise the back at 55 ℃ of following isothermal reaction 30min, temperature is elevated to 80 ℃ then, drips solution (II) again; All dropwise 80 ℃ of isothermal reactions 3 hours, stopped reaction, about 50 ℃ in product Dropwise 5 0%NaOH solution; PH is transferred to weakly alkaline, obtain a kind of reddish-brown transparent liquid, i.e. quaternary phosphorus-free green environment protecting scale inhibitor.
Embodiment 2
(1) gets the 20g maleic anhydride and place beaker, be dissolved in the 25mL water, be heated to and make its abundant hydrolysis under 55 ℃, be chilled to room temperature, add 15mL vinylformic acid wiring solution-forming (I);
(2) get 16g sodium allyl sulfonate and 7g ammonium persulphate and be dissolved in the 25mL water, wiring solution-forming (II);
(3) get the 40g equisetic acid and be dissolved in the 50mL water, temperature is raised to 60 ℃, under agitation drips solution (I); Dropwise the back at 60 ℃ of following isothermal reaction 30min, temperature is elevated to 85 ℃ then, drips solution (II) again; All dropwise 85 ℃ of isothermal reactions 3 hours, stopped reaction, about 50 ℃ in product Dropwise 5 0%NaOH solution; PH is transferred to weakly alkaline, obtain a kind of reddish-brown transparent liquid, i.e. quaternary phosphorus-free green environment protecting scale inhibitor.
Embodiment 3
(1) gets the 18g maleic anhydride and place beaker, be dissolved in the 20mL water, be heated to and make its abundant hydrolysis under 60 ℃, be chilled to room temperature, add 15mL vinylformic acid wiring solution-forming (I);
(2) get 10g sodium allyl sulfonate and 5g ammonium persulphate and be dissolved in the 20mL water, wiring solution-forming (II);
(3) get the 45g equisetic acid and be dissolved in the 60mL water, temperature is raised to 60 ℃, under agitation drips solution (I); Dropwise the back at 60 ℃ of following isothermal reaction 30min, temperature is elevated to 75 ℃ then, drips solution (II) again; All dropwise 75 ℃ of isothermal reactions 4 hours, stopped reaction, about 50 ℃ in product Dropwise 5 0%NaOH solution; PH is transferred to weakly alkaline, obtain a kind of reddish-brown transparent liquid, i.e. quaternary phosphorus-free green environment protecting scale inhibitor.
Embodiment 4
(1) gets the 30g maleic anhydride and place beaker, be dissolved in the 35mL water, be heated to and make its abundant hydrolysis under 55 ℃, be chilled to room temperature, add 25mL vinylformic acid wiring solution-forming (I);
(2) get 20g sodium allyl sulfonate and 10g ammonium persulphate and be dissolved in the 35mL water, wiring solution-forming (II);
(3) get the 65g equisetic acid and be dissolved in the 60mL water, temperature is raised to 55 ℃, under agitation drips solution (I); Dropwise the back at 55 ℃ of following isothermal reaction 30min, temperature is elevated to 85 ℃ then, drips solution (II) again; All dropwise 85 ℃ of isothermal reactions 3 hours, stopped reaction, about 50 ℃ in product Dropwise 5 0%NaOH solution; PH is transferred to weakly alkaline, obtain a kind of reddish-brown transparent liquid, i.e. quaternary phosphorus-free green environment protecting scale inhibitor.
Embodiment 5
(1) gets the 25g maleic anhydride and place beaker, be dissolved in the 30mL water, be heated to and make its abundant hydrolysis under 60 ℃, be chilled to room temperature, add 15mL vinylformic acid wiring solution-forming (I);
(2) get 12g sodium allyl sulfonate and 5g ammonium persulphate and be dissolved in the 25mL water, wiring solution-forming (II);
(3) get the 55g equisetic acid and be dissolved in the 60mL water, temperature is raised to 55 ℃, under agitation drips solution (I); Dropwise the back at 55 ℃ of following isothermal reaction 30min, temperature is elevated to 85 ℃ then, drips solution (II) again; All dropwise 85 ℃ of isothermal reactions 3.5 hours, stopped reaction, about 50 ℃ in product Dropwise 5 0%NaOH solution; PH is transferred to weakly alkaline, obtain a kind of reddish-brown transparent liquid, i.e. quaternary phosphorus-free green environment protecting scale inhibitor.
Embodiment 6
The scale-inhibiting properties test experiments
The static-state scale inhibition performance test methods of lime carbonate, calcium phosphate is measured the scale-inhibiting properties of Scale inhibitors respectively according to GB/T 16632-2008 and GB/T 22626-2008, and the experiment condition of lime carbonate scale inhibition is: Ca
2+Concentration is 250mg/L, HCO
3 -Concentration is 250mg/L, between pH=7～9, and 80 ℃ of temperature, the time is 10h; The experiment condition of calcium phosphate scale inhibition is: Ca
2+Concentration is 250mg/L, PO
4 3-Concentration 5mg/L, 80 ℃ of temperature, the time is 10h, scale-inhibiting properties is as shown in table 1; The static-state scale inhibition performance test methods of permanent white is measured the scale-inhibiting properties of Scale inhibitors according to industry standard SY/T5673-93, and the experiment condition of permanent white scale inhibition is: Ba
2+Concentration is 370mg/L, SO
4 2-Concentration is 540mg/L, between pH=7～9, and 70 ℃ of temperature, the time is 16h, scale-inhibiting properties is as shown in table 1.
Table 3 embodiment scale-inhibiting properties test result
Can find out that from the test-results of table 1 equisetic acid, vinylformic acid, maleic anhydride, sodium allyl sulfonate quadripolymer (AA-AA-MA-SAS) Scale inhibitors that the present invention is prepared are to CaCO
3Scale inhibition effect best, scale inhibition performance is all more than 95%, to Ca during add-on 10mg/L
3(PO
4)
2And BaSO
4Tangible scale-inhibiting properties is also arranged.
Method of use: the Scale inhibitors product is made into 10% aqueous solution, and throwing in scale inhibition dosage is 12～20mg/L, chooses suitable release position according to the production technique needs.
Claims (5)
1. the preparation method of a phosphorus-free green environment protecting scale inhibitor is characterized in that: comprise the steps:
(1) with maleic anhydride be dissolved in account for water inventory 35～50% between, under 50～60 ℃, make its abundant hydrolysis, be chilled to room temperature maleic anhydride solution by volume again: vinylformic acid is 1: 0.5～0.7 wiring solution-forming (I);
(2) with sodium allyl sulfonate and ammonium persulphate by mass ratio be example be dissolved in account for water inventory 35～50% between, wiring solution-forming (II);
(3) equisetic acid is dissolved in the remainder water, temperature is raised to 50～60 ℃, under agitation drips solution (I) (dripping speed control dropwises in 30min); Dropwise the back at 50～60 ℃ of following isothermal reaction 30min, temperature is elevated to 75～85 ℃ then, drips solution (II) again; All dropwise 75～85 ℃ of isothermal reactions 3～4 hours; Stopped reaction, about 50 ℃ in product Dropwise 5 0%NaOH solution, pH is transferred to weakly alkaline; Obtain a kind of reddish-brown transparent liquid, i.e. quaternary phosphorus-free green environment protecting scale inhibitor.
2. the preparation method of a kind of phosphorus-free green environment protecting scale inhibitor according to claim 1 is characterized in that: be made up of equisetic acid, vinylformic acid, maleic anhydride, sodium allyl sulfonate, ammonium persulphate and water.The mass ratio of each component is preferably: equisetic acid 25～40, vinylformic acid 8～20, maleic anhydride 12～18, sodium allyl sulfonate 6～12, ammonium persulphate 3～7, water 130～220.
3. preparation method according to claim 1, its characteristics are that the maleic anhydride hydrolysis temperature is 50～60 ℃.
4. preparation method according to claim 1, its characteristics are that polymeric reaction temperature is 75～85 ℃.
5. preparation method according to claim 1, its characteristics are that maleic anhydride liquor capacity and acrylic acid volume ratio are between 1: 0.5～1: 0.7 after the hydrolysis.
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| CN103820150A (en) * | 2014-03-14 | 2014-05-28 | 西安石油大学 | Barium sulfate and strontium sulfate descaling agent and preparation method thereof |
| CN104163482A (en) * | 2014-09-02 | 2014-11-26 | 南通正源环保科技有限公司 | Multifunctional environment-friendly antiscale dispersing agent |
| CN104174295A (en) * | 2014-09-15 | 2014-12-03 | 山东天庆科技发展有限公司 | Phosphorus-free reverse osmosis scale inhibitor and preparation method thereof |
| CN106103510A (en) * | 2014-03-25 | 2016-11-09 | 墨西哥石油研究院 | Derive from the preparation method of the ternary atactic copolymer of itaconic acid and equisetic acid and/or its isomer and/or sodium olefin sulfonate and the purposes of products therefrom |
| CN112920296A (en) * | 2021-02-01 | 2021-06-08 | 西南石油大学 | Dispersing agent for dissolving barium sulfate scale and preparation method thereof |
| CN118374270A (en) * | 2024-06-21 | 2024-07-23 | 西安三维科技发展有限责任公司 | Scale and corrosion inhibition and wax control integrated treatment agent and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103820150A (en) * | 2014-03-14 | 2014-05-28 | 西安石油大学 | Barium sulfate and strontium sulfate descaling agent and preparation method thereof |
| CN106103510A (en) * | 2014-03-25 | 2016-11-09 | 墨西哥石油研究院 | Derive from the preparation method of the ternary atactic copolymer of itaconic acid and equisetic acid and/or its isomer and/or sodium olefin sulfonate and the purposes of products therefrom |
| CN106103510B (en) * | 2014-03-25 | 2019-07-09 | 墨西哥石油研究院 | Ternary atactic copolymer, its preparation method and purposes |
| CN104163482A (en) * | 2014-09-02 | 2014-11-26 | 南通正源环保科技有限公司 | Multifunctional environment-friendly antiscale dispersing agent |
| CN104174295A (en) * | 2014-09-15 | 2014-12-03 | 山东天庆科技发展有限公司 | Phosphorus-free reverse osmosis scale inhibitor and preparation method thereof |
| CN112920296A (en) * | 2021-02-01 | 2021-06-08 | 西南石油大学 | Dispersing agent for dissolving barium sulfate scale and preparation method thereof |
| CN118374270A (en) * | 2024-06-21 | 2024-07-23 | 西安三维科技发展有限责任公司 | Scale and corrosion inhibition and wax control integrated treatment agent and preparation method thereof |
| CN118374270B (en) * | 2024-06-21 | 2024-09-03 | 西安三维科技发展有限责任公司 | Scale and corrosion inhibition and wax control integrated treatment agent and preparation method thereof |
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Application publication date: 20120222 |