CN1128764C - Corrosion-retarding compound scaling inhibitor for treating middle- or high-hardness circulating water - Google Patents
Corrosion-retarding compound scaling inhibitor for treating middle- or high-hardness circulating water Download PDFInfo
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- CN1128764C CN1128764C CN 00109589 CN00109589A CN1128764C CN 1128764 C CN1128764 C CN 1128764C CN 00109589 CN00109589 CN 00109589 CN 00109589 A CN00109589 A CN 00109589A CN 1128764 C CN1128764 C CN 1128764C
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- acid
- sulfonic acid
- composite slow
- corrosion scale
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Abstract
The present invention relates to a compounded corrosion and scale inhibitor for treating circulating water with middle and high hardness. The present invention comprises 1 to 40% of organic phosphino carboxylic acid containing sulfonic acid, 1 to 20% of acrylic acid copolymers, 1 to 30% of organic phosphonic acid compound, 1 to 30% of zinc salts and 30 to 80% of water on the basis of the total weight of the compounded agent. By adopting the novel phosphino carboxylic acid compound containing the sulfonic acid, the compounded agent of the present invention has the advantages of greatly improved scale inhibition performance of calcium carbonate and calcium phosphate on those of common organic phosphonic acid, the function of corrosion inhibition and low phosphorus content, and further comes up to the requirements of environmental protection.
Description
Technical field
The present invention relates to be used for handling the water conditioner of high rigidity recirculated water.
Technical background
Most of water quality of northern China belongs to middle high-hardness water, and the outstanding feature of this class water quality is that calcium hardness is that 60-250mg/L is (with CaCO
3Meter, down together), total alkalinity is that 80-250mg/L is (with CaCO
3Meter, down together).Because basicity and hardness are all higher, the index of stability of water is less than 6, and the corrosion tendency of water body is little, and fouling tendency is big, shows as the deposition of calcium dirt in the actual motion.
Handle the method for this class water quality the seventies, the main employing adds acid and reduces basicity in the water, adds medicament such as Sodium hexametaphosphate 99 simultaneously and handles.This method treatment effect in actual motion is unsatisfactory, complicated operation, and management inconvenience, hyper acid if add, and then equipment corrosion quickens, and hypoacidity otherwise add, and then the fouling of equipment is difficult to control again.
US4,744,949 and EP0238,728 disclose the prescription that contains resistance calcium phosphate scale scale inhibitor poly phosphonate, and treatment effect is better.But, can cause the eutrophication pollution of water body owing to the polyphosphonate facile hydrolysis.
Adopt all-organic formula the eighties, as include the prescription of machine phosphonic acid, polymkeric substance and zinc, the high-hardness water effect is better in the processing.Organic phospho acid had both played corrosion inhibition, the effect of resistance calcium carbonate scale is arranged again, and overcome the pollution of polyphosphonate to environment to a certain extent.But the effect of organic phospho acid commonly used such as the resistance calcium phosphate scale of ATMP, HEDP and PBTC is all very poor, needs the good polymkeric substance of composite resistance calcium phosphate scale.Type of polymer difference, treatment effect are also different, and often cost is also higher and hinder the good polymkeric substance of calcium phosphate scale.On the other hand, polymkeric substance easily and quaternary ammonium salt type bactericidal agent effect and reduce drug effect.
Summary of the invention
The present invention is intended to overcome the shortcoming of prior art, provides a kind of and has resistance calcium phosphate and calcium carbonate scale performance simultaneously, and only contain the composite slow-corrosion scale resistor prescription of small amount of polymer.
The component of recombiner provided by the invention comprises the organic phosphine carboxylic acid Scale inhibitors that contains sulfonic acid, organic phospho acid inhibiter, polymer dispersant and water.With the recombiner gross weight is benchmark, and each component concentration is: contain the organic phosphine carboxylic acid 1～40% of sulfonic acid, preferred 5～30%; Acrylic copolymer 1～20%, preferred 4～12%; Organic phospho acid compound 1～30%, preferred 2～20%; Zinc salt (in zinc) 1～30%, preferred 5～20%; Water 30～80%, preferred 40～70%.The described organic phosphine carboxylic acid that contains sulfonic acid is homemade product, and its structural formula is:
Wherein n is 2～16 integer, preferred 2～12 integer, more preferably 2-phosphino--5-sulfonic acid-1,2-dicarboxylic acid-pentane (being called for short PSPD), 2-phosphino--6-sulfonic acid-1,2-dicarboxylic acid-hexane (being called for short PSHD), 2-phosphino--7-sulfonic acid-1,2 dicarboxylic acid-heptane (being called for short PSHPD), 2-phosphino--8-sulfonic acid-1,2-dicarboxylic acid-octane (being called for short PSOD) and 2-phosphino--12-sulfonic acid-1,2-dicarboxylic acid-dodecane (being called for short PSDD) etc.
Described acrylic copolymer, it can be vinylformic acid/2-acrylamido-2-methyl propane sulfonic acid multipolymer, vinylformic acid/maleic acid, vinylformic acid/toxilic acid/2-acrylamido-2-methyl propane sulfonic acid multipolymer, vinylformic acid/3 acrylic acid ester-2-hydroxy-propanesulfonic acid multipolymer, vinylformic acid/Propylene glycol monoacrylate multipolymer, vinylformic acid/3 acrylic acid ester-2-hydroxy-propanesulfonic acid multipolymer and vinylformic acid/allyl group phosphonic acid copolymer.
Described organic phospho acid compound is selected from amido three methene phosphonic acids (ATMP), ethylene diamine tetra methylene phosphonic acid (EDTMP), 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP) and their sylvite, sodium salt, ammonium salt etc.
Described zinc salt is zinc chloride or zinc sulfate.
Recombiner of the present invention also can contain nitrogen azole material, and its content is 0～5%.Described nitrogen azole material can be benzotriazole (BZT), mercaptobenzothiazole (MBT).Such material has effect preferably to suppressing copper corrosion.
Recombiner of the present invention can also contain solubility promoter, and its add-on is 0～5%.Described solubility promoter is selected from glacial acetic acid, materials such as dimethyl formamide and ethanol.With the performance solublization, make recombiner easier to be composite.
The working concentration of recombiner of the present invention in recirculated water can be 0.1～100mg/L, preferred 10～60mg/L.
The described organic phosphine carboxylic acid compound that contains sulfonic acid can prepare as follows:
(1) make phosphonous acid alkyl ester and toxilic acid alkyl ester in the presence of excessive alkyl carboxylic acid at 0～150 ℃, preferred 20～100 ℃ the reaction 5～30 hours, preferred 10～20 hours, underpressure distillation obtained intermediate phosphine carboxylicesters.Alkyl in said alkyl ester and the alkyl carboxylic acid is identical or different C
1～C
5Straight chain or band branched-chain alkyl, preferred C
1～C
3Alkyl.
(2) under the existence of aprotic solvent, make intermediate phosphine carboxylicesters and alkalimetal hydride and saturated dihalide at 0～150 ℃, preferred 20～100 ℃, reacted 0.5～10 hour, preferred 2～6 hours,, obtain halogenated phosphine carboxylicesters with product washing, dry, purification.The mechanism of this step reaction is that the phosphine carboxylicesters reacts with alkalimetal hydride earlier, sloughs a hydrogen atom, generates an alkali metal salt of phosphine carboxylicesters, with the saturated dihalide reaction, generates halogenated phosphine carboxylicesters again.Therefore, saturated dihalide can add reaction system simultaneously with alkalimetal hydride, also can add reaction system later on.In addition, consider exothermic heat of reaction, intermediate phosphine carboxylicesters preferably is added drop-wise in the reaction system.
Preferred dichloro-alkane of said saturated dihalide and two bromoalkanes, alkyl wherein is C
2～C
16, preferred C
2～C
12Alkyl.Said alkalimetal hydride can be NaH, KH or LiH.Said aprotic solvent can be benzene,toluene,xylene, N, dinethylformamide (DMF), N,N-dimethylacetamide etc.
(3) make halogenated phosphine carboxylicesters and S-WAT or sodium bisulfite in the presence of water, at 20～120 ℃, preferred 50～100 ℃, reacted 2～48 hours, preferred 2～24 hours, obtain sulfonated phosphine carboxylicesters.S-WAT or sodium bisulfite are suitable excessive 10%～50%, so that react completely.After having reacted, available weak base quaternary anionite-exchange resin separates purification.
(4) with sulfonated phosphine carboxylicesters under the concentrated hydrochloric acid effect, hydrolysis is 10～70 hours under reflux state, preferred 20～40 hours, the alcohol of excessive hydrochloric acid and generation was removed in underpressure distillation, obtained final product-the contain organic phosphine carboxylic acid of sulfonic acid.
The present invention has the following advantages:
1. adopt the novel phosphine carboxylic acid cpd that contains sulfonic acid, its resistance calcium carbonate scale and resistance calcium phosphate scale performance all improve a lot than organic phospho acid commonly used, have corrosion inhibition concurrently, and phosphorus content are low, more compliance with environmental protection requirements.When other component is identical, adopts the prescription resistance carbon dirt rate of the phosphine carboxylic acid that contains sulfonic acid and resistance phosphorus dirt rate to be respectively 87% and 95%, and adopt the resistance carbon dirt rate and the resistance phosphorus dirt rate of the prescription of PBTC to be respectively 78% and 57%.
2. when reaching similar effect, the usage quantity of polymkeric substance significantly reduces in the recombiner of the present invention, is about half of existing prescription.
Embodiment
Embodiment 1
Present embodiment is a 2-phosphino--1, the preparation of 2-dicarboxylic acid-6-sulfonic acid hexane (PSHD).
Get the 500ml four-hole bottle, add dimethyl maleate 358g (2.49mol), Glacial acetic acid 180g, be warming up to 60 ℃ under stirring, drip trimethyl phosphite 333g, control reaction temperature insulation 24 hours, the methyl acetate and the excessive glacial acetic acid of generation removed in underpressure distillation, gets intermediate.
In the 500ml four-hole bottle, 41g intermediate (0.16mol) is added drop-wise among the 13.6g KH (0.176mol) that is suspended in the toluene (250ml), stirred 30 minutes under the room temperature, add 52g dibromobutane (0.24mol), temperature rising reflux 4 hours.Reaction mixture is used 2%H
2SO
4MgSO is used in washing
4Drying, light constituent is removed in underpressure distillation, gets the halogenated phosphine carboxylicesters of 25g.
In the 100ml there-necked flask, add the halogenated phosphine carboxylicesters of 13g (0.031mol), 5.8gNa
2SO
3(0.046mol), refluxed 5 hours, must clarify yellow liquid, be sulfonated phosphine carboxylicesters with 42g water.Add the 15ml concentrated hydrochloric acid, refluxed 40 hours, get clear liquor.Remove the methyl alcohol of HCl and generation through underpressure distillation, get product P SHD.
With different saturated dihalides is raw material, can prepare the phosphine carboxylic acid cpd that other contains sulfonic acid.
Embodiment 2
The preparation of recombiner: with 8 gram PSOD, 8 gram HEDP, 10 gram zinc sulfate, 8 gram vinylformic acid and 2-acrylamido-2-methyl propane sulfonic acid multipolymer (trade mark RP-33, Beijing woods China water stabilizer factory produces) and 66 gram H
2O joins in the 250ml beaker successively, stirs and promptly gets required recombiner.The dosage of used single agent calculates by pure product, down together.
Water quality: the hard 60mg/L of calcium, total alkali 80mg/L.
Adopt above-mentioned recombiner and water quality to carry out the experiment of static state resistance calcium carbonate scale, with reference to No. the 401st, China Petroleum Chemicals Corporation's " water coolant analysis and test method ", 80 ℃ of experiment water temperatures concentrate 2 times.Experimental result sees Table 1.
Adopt above-mentioned recombiner and water quality to carry out the experiment of static state resistance calcium phosphate scale, with reference to No. the 402nd, China Petroleum Chemicals Corporation's " water coolant analysis and test method ", 80 ℃ of experiment water temperatures left standstill 10 hours.Experimental result sees Table 1.
Adopt above-mentioned recombiner and water quality to be rotated the lacing film corrosion experiment, with reference to HG/T 2159-91 standard, 80 ℃ of experiment water temperatures, 75 rev/mins of rotating speeds move 96 hours.Experimental result sees Table 1.
Embodiment 3
Recombiner is formed: with 26 gram PSOD, and 13 gram HEDP, 17 gram zinc sulfate, 7 gram RP-33,37 gram H
2O.
Water quality: the hard 104mg/L of calcium, total alkali 130mg/L.
Adopt above-mentioned recombiner and water quality to carry out the experiment of static state resistance calcium carbonate scale respectively according to the method for embodiment 2, experiment of static resistance calcium phosphate scale and rotary hanging plate corrosion experiment the results are shown in Table 1.
Embodiment 4
Recombiner is formed: with 25 gram PSHD, and 5 gram HEDP, 12 gram zinc sulfate, 10 gram vinylformic acid and allyl group phosphonic acid copolymer (trade mark RP-92, Beijing woods China water stabilizer factory produces), 48 gram H
2O.
Water quality: the hard 235mg/L of calcium, total alkali 125mg/L.
Adopt above-mentioned recombiner and water quality to carry out the experiment of static state resistance calcium carbonate scale respectively according to the method for embodiment 2, experiment of static resistance calcium phosphate scale and rotary hanging plate corrosion experiment the results are shown in Table 1.
Embodiment 5
Recombiner is formed: with 20 gram PSHPD, and 4 gram HEDP, 8 gram zinc chloride, 8 gram vinylformic acid and toxilic acid and 2-acrylamido-2-methyl propane sulfonic acid multipolymer (trade mark RP-31, Beijing woods China water stabilizer factory produces), 60 gram H
2O.
Water quality: the hard 245mg/L of calcium, total alkali 240mg/L.
Adopt above-mentioned recombiner and water quality to carry out the experiment of static state resistance calcium carbonate scale respectively according to the method for embodiment 2, experiment of static resistance calcium phosphate scale and rotary hanging plate corrosion experiment the results are shown in Table 1.
Comparative Examples 1
This Comparative Examples host adopts PBTC, contrasts with embodiment 2.
Recombiner is formed: 8 gram PBTC, 8 gram HEDP, 10 gram zinc sulfate, 8 gram RP-33,66 gram H
2O.
Water quality: the hard 60mg/L of calcium, total alkali 80mg/L.
Adopt above-mentioned recombiner and water quality to carry out the experiment of static state resistance calcium carbonate scale respectively according to the method for embodiment 2, experiment of static resistance calcium phosphate scale and rotary hanging plate corrosion experiment the results are shown in Table 1.
Comparative Examples 2
This Comparative Examples host adopts PBTC, contrasts with embodiment 2.
Recombiner is formed: change 8 gram RP-33 into 16 gram RP-33,66 gram H
2O changes 58 gram water into, and all the other are with Comparative Examples 1.
Water quality: the hard 60mg/L of calcium, total alkali 80mg/L.
Adopt above-mentioned recombiner and water quality to carry out the experiment of static state resistance calcium carbonate scale respectively according to the method for embodiment 2, experiment of static resistance calcium phosphate scale and rotary hanging plate corrosion experiment the results are shown in Table 1.
Table 1
| Recombiner | Consumption (mg/L) | Resistance carbon dirt rate (%) | Resistance phosphorus dirt rate (%) | Erosion rate (mdd) |
| Embodiment 2 | 50 | 87 | 99 | 1.79 |
| Embodiment 3 | 30 | 84.5 | 93 | 1.44 |
| Embodiment 4 | 40 | 78 | 90 | 1.12 |
| Embodiment 5 | 50 | 75 | 90 | 0.99 |
| Comparative Examples 1 | 50 | 78 | 57 | 1.85 |
| Comparative Examples 2 | 50 | 85 | 95 | 1.70 |
As can be seen from Table 1, when other component is identical, the present invention adopts the prescription resistance carbon dirt rate of the phosphine carboxylic acid that contains sulfonic acid and resistance phosphorus dirt rate obviously to improve than dirty rate of the resistance carbon of the prescription that adopts PBTC and resistance phosphorus dirt rate, when the two effect was close, the usage quantity of polymkeric substance had only half of the latter in the recombiner of the present invention.
Embodiment 6
Present embodiment is a dynamic simulation experiment.
Recombiner is formed: with 20 gram PSOD, and 4 gram ATMP, 8 gram zinc chloride, 8 gram RP-33,1 gram BZT, 59 gram H
2O.
Experimental technique carries out with reference to the HG/T2160-91 standard.Water quality is circulating water system, the hard 235mg/L of calcium, total alkali 250mg/L.Recombiner add-on 50mg/L.
Experimental result: the erosion rate 0.041mm/a of test tube adheres to speed 0.78mcm.
Claims (10)
1. composite slow-corrosion scale resistor that is used for handling high rigidity recirculated water, with the recombiner gross weight is benchmark, comprising: contain the organic phosphine carboxylic acid 1～40% of sulfonic acid, acrylic copolymer 1～20%, organic phospho acid compound 1～30%, zinc salt 1～30% and water 30～80%.
2. composite slow-corrosion scale resistor according to claim 1 is characterized in that comprising: contain the organic phosphine carboxylic acid 5～30% of sulfonic acid, acrylic copolymer 4～12%, organic phospho acid compound 2～20%, zinc salt 5～20% and water 40～70%.
3. composite slow-corrosion scale resistor according to claim 1 is characterized in that the described organic phosphine carboxylic acid that contains sulfonic acid has following structure:
Wherein n is 2～16 integer.
4. composite slow-corrosion scale resistor according to claim 3 is characterized in that n is 2～12 integer.
5. according to claim 1 or 3 described composite slow-corrosion scale resistors, it is characterized in that the described organic phosphine carboxylic acid that contains sulfonic acid is selected from 2-phosphino--5-sulfonic acid-1,2-dicarboxylic acid-pentane, 2-phosphino--6-sulfonic acid-1,2-dicarboxylic acid-hexane, 2-phosphino--7-sulfonic acid-1,2 dicarboxylic acid-heptane, 2-phosphino--8-sulfonic acid-1,2-dicarboxylic acid-octane and 2-phosphino--12-sulfonic acid-1,2-dicarboxylic acid-dodecane.
6. composite slow-corrosion scale resistor according to claim 1, it is characterized in that described acrylic copolymer is selected from vinylformic acid and 2-acrylamido-2-methyl propane sulfonic acid multipolymer, vinylformic acid and maleic acid, vinylformic acid and toxilic acid and 2-acrylamido-2-methyl propane sulfonic acid multipolymer, vinylformic acid and 3 acrylic acid ester-2-hydroxy-propanesulfonic acid multipolymer, vinylformic acid and Propylene glycol monoacrylate multipolymer, vinylformic acid and 3 acrylic acid ester-2-hydroxy-propanesulfonic acid multipolymer and vinylformic acid and allyl group phosphonic acid copolymer.
7. composite slow-corrosion scale resistor according to claim 1 is characterized in that described organic phospho acid compound is selected from amido three methene phosphonic acids, ethylene diamine tetra methylene phosphonic acid, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid and their sylvite, sodium salt and ammonium salt.
8. composite slow-corrosion scale resistor according to claim 1 is characterized in that described zinc salt is zinc chloride or zinc sulfate.
9. composite slow-corrosion scale resistor according to claim 1 is characterized in that also containing the nitrogen azole material that is selected from benzotriazole or mercaptobenzothiazole, and its content is 0～5%.
10. composite slow-corrosion scale resistor according to claim 1 is characterized in that also containing and is selected from glacial acetic acid, dimethyl formamide and alcoholic acid solubility promoter, and its add-on is 0～5%.
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|---|---|---|---|
| CN 00109589 CN1128764C (en) | 2000-06-28 | 2000-06-28 | Corrosion-retarding compound scaling inhibitor for treating middle- or high-hardness circulating water |
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|---|---|---|---|
| CN 00109589 CN1128764C (en) | 2000-06-28 | 2000-06-28 | Corrosion-retarding compound scaling inhibitor for treating middle- or high-hardness circulating water |
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| CN1331051A CN1331051A (en) | 2002-01-16 |
| CN1128764C true CN1128764C (en) | 2003-11-26 |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1307113C (en) * | 2004-02-11 | 2007-03-28 | 北京拓凯化工技术有限公司 | Environmental-protection high-efficiency low-phosphonic scale inhibitor composition and its preparation method and use |
| JP4725513B2 (en) * | 2004-05-25 | 2011-07-13 | 栗田工業株式会社 | Cooling water treatment method |
| CN100357331C (en) * | 2005-06-15 | 2007-12-26 | 北京博泰盛合科技有限公司 | Copolymer and its preparation method and reverse osmosis membrane protective agent comprising the copolymer and its uses |
| CN101368091B (en) * | 2007-08-16 | 2012-01-11 | 中国石油天然气集团公司 | Oil well cement retarder |
| CN102408879A (en) * | 2010-09-23 | 2012-04-11 | 中国石油化工集团公司 | Sodium chloride aqueous solution coolant |
| CN102732892B (en) * | 2011-04-11 | 2013-11-06 | 中国石油化工股份有限公司 | Metal corrosion inhibitor composition, metal corrosion inhibitor thereof and application thereof |
| CN102786158B (en) * | 2011-05-20 | 2014-10-29 | 中国石油化工股份有限公司 | Corrosion-inhibition scale inhibitor composition and corrosion-inhibition scale inhibitor and application thereof |
| CN103058400A (en) * | 2012-12-17 | 2013-04-24 | 青岛森淼实业有限公司 | Water softening ball and preparation method thereof |
| CN104402127B (en) * | 2014-12-02 | 2016-03-23 | 天津开广工业水处理有限公司 | A kind of oil field special corrosion and scale inhibitor |
| CN104610221B (en) * | 2015-01-19 | 2016-11-30 | 烟台海川化学制品有限公司 | A kind of preparation method of 1 acrylic 1,3 sultones |
| CN106673218A (en) * | 2015-11-10 | 2017-05-17 | 宜兴全泽化工有限公司 | Green phosphorus-free anti-scale corrosion inhibitor |
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