CN1331050A - Corrosion-retarding compound scaling inhibitor for treating circulating low-hardness water - Google Patents

Corrosion-retarding compound scaling inhibitor for treating circulating low-hardness water Download PDF

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CN1331050A
CN1331050A CN00109590A CN00109590A CN1331050A CN 1331050 A CN1331050 A CN 1331050A CN 00109590 A CN00109590 A CN 00109590A CN 00109590 A CN00109590 A CN 00109590A CN 1331050 A CN1331050 A CN 1331050A
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acid
phosphino
recombiner
sulfonic acid
water
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CN1124992C (en
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王振宇
李本高
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F14/00—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes
    • C23F14/02—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes by chemical means
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

A corrosion-retarding compound scaling inhibitor for treating the circulated low-hardness coding water contains sulfonic acid contained phosphincarboxylic acid (1-30 wt.%), hydroxyphosphinoacetic acid compound (5-40%), organic phosphonic acid compound (1-12%), zinc salt (1-20%) and water (30-80%). Its advantages include high anti-scaling effect, no deposit of calcium phosphate, and less nutrient-enriching pollution of water.

Description

A kind of composite slow-corrosion scale resistor of handling circulating low-hardness water
The present invention relates to a kind of water conditioner of handling circulating low-hardness water.
For industrial circulating cooling water system, different water quality causes the degree difference of metallic corrosion, and the index of stability (IR) of the corrosion of water quality and fouling tendency used water is weighed.6.0＜IR＜7.5 belong to corrodibility water quality, IR＞7.5 belong to severe corrosive water quality.The most of geographic water quality in China south belongs to soft, low basicity water quality, and the calcium in the water is hard＜60mg/L, basicity＜80mg/L, pH is about 7, and index of stability IR＞7.5 belong to severe corrosive water quality.The water quality calcium of certain areas is hard＜20mg/L, and basicity＜60mg/L, total dissolved solidss content 66～100mg/L, index of stability IR＞9.0 belong to extremely strong corrodibility water quality.These water quality are stronger to corrosion of Carbon Steel, if deal with improperly, can cause the heavy corrosion of equipment.
Use the water quality effect of this class severe corrosive of chromate treating better in history, but chromic salt is poisonous, has been forbidded strictly to use.It is main inhibiter with poly-phosphate that Mccoy JW proposes a kind of in " The chemical treatment of coolingwater " (NALCO, 1974) literary composition, the prescription of composite organic phospho acid and polyphosphoric acid.This method in use in order to obtain treatment effect preferably, need be replenished the calcium, and in order to prevent the calcium phosphate scale precipitation, also will add acid.If manage properly, have the good treatment effect, but when management and operation were made a fault, treatment effect just descended significantly.
Chinese patent CN1176229 discloses the prescription that contains hydroxyl phosphino-acetate, organic phospho acid, organic phosphine carboxylic acid and zinc, need not replenish the calcium in the use, and is easy to operate, and treatment effect is also fine.But the organic phospho acid and the resistance calcium phosphate scale and the dissemination of organic phosphine carboxylic acid in the prescription are all very poor, show as the water treatment of extremely low basicity and hardness effectively, and when the hardness of water quality and basicity were high slightly, the adhesion speed of part test tube was understood higher.If in prescription, add the good polymkeric substance of resistance calcium phosphate scale, then can improve the effect and the dispersion effect of resistance calcium phosphate scale, but can bring composite difficulty, and can influence the activity of cats product type sterilant.
The purpose of this invention is to provide a kind of prescription that does not contain polymkeric substance, can be used for handling the water quality of soft, low basicity, its resistance calcium phosphate scale performance and dispersing property significantly improve than prior art.
Composite slow-corrosion scale resistor provided by the invention comprises the phosphine carboxylic acid cpd that contains sulfonic acid, hydroxyl phosphino-acetic acid compound, organic phospho acid compound and zinc salt, its component concentration (is 100% in recombiner weight): contain the phosphine carboxylic acid 1～30% of sulfonic acid, preferred 5～25%; Hydroxyl phosphino-acetic acid compound 5～40%, preferred 10～35%; Organic phospho acid compound 1～12%, preferred 2～8%; Zinc salt (in zinc) 1～20%, preferred 2～10%; Water 30～80%, preferred 40～70%.
The described organic phosphine carboxylic acid that contains sulfonic acid is homemade product, and its structural formula is:
Figure A0010959000041
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 hydroxyl phosphino-acetic acid compound is another host of this recombiner, can be 2-hydroxyl phosphino-acetate (HPAA), and sylvite, and sodium salt and ammonium salt, this compounds are a kind of high-efficient corrosion inhibitors.
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.Solubilizing agent can be brought into play solublization, makes 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) in the presence 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.
Recombiner component hydroxyl phosphino-acetate of the present invention, organic phospho acid is the commercially available prod, and the organic carboxylic acid of seeing that contains sulfonic acid is homemade product, and above-mentioned substance all exists with the form of the aqueous solution.When composite, only need at normal temperatures each component to be joined in the container successively in given ratio, stirring gets final product.
The present invention has the following advantages:
1. use efficient scale inhibitor-the contain organic phosphine carboxylic acid of sulfonic acid, this agent not only has good resistance calcium carbonate scale performance, and good resistance calcium phosphate scale performance arranged, when other component is identical, adopt the adhesion speed of the prescription of this Scale inhibitors only to be 0.85mcm, and the adhesion speed of the prescription of employing PBTC is up to 5.93mcm.
2. the present invention does not contain polymkeric substance, and composite good stability is compared with the existing prescription that does not contain polymkeric substance easily, and handling soft and low basicity water quality has better scale inhibition dispersion effect.
3. recombiner of the present invention does not contain inorganic phosphate, can prevent the calcium phosphate scale precipitation, reduces water eutrophication and pollutes, and do not contain deleterious chromic salt, helps environment protection.
4. adopt recombiner cycle of treatment water coolant of the present invention, can directly it be joined in the recirculated water pipe network, do not need pre-treatment, simple to operate, management easily.
Further specify characteristics of the present invention below by 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
Present embodiment is the corrosion of carbon steel experiment.
The preparation of recombiner: with 30 gram HPAA, 10 gram PSOD, 4 gram ATMP, 10 gram ZnCl 2, 46 gram H 2O joins in the 250ml beaker successively, stirs and promptly gets required recombiner
Water quality: calcium hardness 18mg/L, magnesium hardness 16mg/L, total alkalinity 50mg/L.
With reference to the HG/T2159-91 standard, adopt above-mentioned recombiner and water quality to be rotated the lacing film corrosion experiment, 80 ℃ of experiment water temperatures, 75 rev/mins of rotating speeds move 96 hours, recombiner add-on 50mg/L.
Experimental result: the erosion rate of test piece is 0.030mm/a.
Embodiment 3
Present embodiment is the corrosion of carbon steel experiment.
The proportioning of recombiner: 15 gram HPAA, 20 gram PSOD, 4 gram HEDP, 4 gram ZnSO 4, 57 gram H 2O.
Water quality: calcium hardness 55mg/L, magnesium hardness 20mg/L, total alkalinity 60mg/L.
Experimental technique is with embodiment 2, recombiner add-on 50mg/L.
Experimental result: the erosion rate of test piece is 0.045mm/a.
Embodiment 4
Present embodiment is the red copper corrosion experiment.
The proportioning of recombiner: 15 gram HPAA, 15 gram PSOD, 2 gram EDTMP, 4 gram ZnSO 4, 4.5 gram BZT, 59.5 gram H 2O.
Water quality: calcium hardness 40mg/L, magnesium hardness 16mg/L, total alkalinity 50mg/L.
Experimental technique is with embodiment 2, recombiner add-on 50mg/L.
Experimental result: the erosion rate of test piece is 0.0037mm/a.
Embodiment 5
Present embodiment is a dynamic simulation experiment, and experimental technique is with reference to the HG/T2160-91 standard.Water quality is circulating water system, calcium hardness 30mg/L wherein, and total alkalinity 50mg/L, pH=6.5-7.5, the replicate(determination) of four φ 10 * 530mm carbon steel test tubes, water is walked tube side, 32-37 ℃ of experiment control inlet water temperature, 10 ℃ of the temperature difference concentrate 2 times, test 20 days.
The proportioning of recombiner: 15 gram HPAA, 20 gram PSOD, 2 gram EDTMP, 7.5 gram ZnSO 4, 55.5 gram H 2O.
Experimental result sees Table 1.
Embodiment 6
Present embodiment is a dynamic simulation experiment, and experimental technique is with reference to the HG/T2160-91 standard.Water quality is circulating water system, calcium hardness 50mg/L wherein, and total alkalinity 60mg/L, all the other conditions are with embodiment 5.
The proportioning of recombiner: 10 gram HPAANa, 20 gram PSODNa, 4 gram HEDPNa, 4 gram ZnSO 4, 62 gram H 2O.
Experimental result sees Table 1.
Embodiment 7
Present embodiment is a dynamic simulation experiment, carries out with reference to the HG/T2160-91 standard.Water quality is circulating water system, calcium hardness 55mg/L wherein, and total alkalinity 50mg/L, all the other conditions are with embodiment 5.
The proportioning of recombiner: 15 gram HPAA, 20 gram PSHD, 2 gram HEDP, 4 gram ZnSO 4, 2.5 gram BZT, 56.5 gram H 2O.
Experimental result sees Table 1.
Embodiment 8
Present embodiment is a dynamic simulation experiment, carries out with reference to the HG/T2160-91 standard.Water quality is circulating water system, calcium hardness 60mg/L wherein, and total alkalinity 50mg/L, all the other conditions are with embodiment 5.
The proportioning of recombiner: 12 gram HPAA, 20 gram PSHPD, 4 gram ATMP, 4 gram ZnCl 2, 1 gram BZT, 59 gram H 2O.
Experimental result sees Table 1.
Comparative Examples
Experimental technique is with reference to embodiment 5.
The proportioning of recombiner: 15 gram HPAA, 20 gram PBTC, 2 gram EDTMP, 7.5 gram ZnSO 4, 55.5 gram H 2O.
Experimental result sees Table 1.Table 1
Recombiner Consumption (mg/L) Erosion rate (mm/a) Adhere to speed (mcm)
Comparative Examples ????50 ????0.042 ????5.93
Embodiment 5 ????50 ????0.037 ????0.85
Embodiment 6 ????60 ????0.041 ????0.70
Embodiment 7 ????60 ????0.043 ????1.1
Embodiment 8 ????50 ????0.050 ????0.92

Claims (10)

1. being used to handle the composite slow-corrosion scale resistor of soft recirculated cooling water, is 100% in recombiner weight, comprising: the phosphine carboxylic acid 1～30% that contains sulfonic acid, hydroxyl phosphino-acetic acid compound 5～40%, organic phospho acid compound 1～12%, zinc salt (in zinc) 1～20%, water 30～80%.
2. recombiner according to claim 1 is characterized in that comprising: contain the phosphine carboxylic acid 5～25% of sulfonic acid, hydroxyl phosphino-acetic acid compound 10～35%, organic phospho acid compound 2～8%, zinc salt 2～10%, water 40～70%.
3. recombiner according to claim 1 and 2 is characterized in that the described organic phosphine carboxylic acid that contains sulfonic acid has following structure:
Figure A0010959000021
Wherein n is 2～16 integer.
4. recombiner according to claim 3 is characterized in that n is 2～12 integer.
5. recombiner according to claim 1 and 2, 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. recombiner according to claim 1 is characterized in that described hydroxyl phosphino-acetic acid compound is selected from 2-hydroxyl phosphino-acetate, and sylvite, sodium salt and ammonium salt.
7. recombiner 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. recombiner according to claim 1 is characterized in that described zinc salt is zinc chloride or zinc sulfate.
9. recombiner 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. recombiner 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%.
CN00109590A 2000-06-28 2000-06-28 Corrosion-retarding compound scaling inhibitor for treating circulating low-hardness water Expired - Lifetime CN1124992C (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100460564C (en) * 2005-10-31 2009-02-11 中国石油化工股份有限公司 Method for restraining corrosion by circulating cooling water of containing sulphur
CN102718329A (en) * 2012-06-28 2012-10-10 山东省泰和水处理有限公司 Composite corrosion inhibition antisludging agent for ultralow rigidity circulation cooling water and preparation method thereof
CN103803731A (en) * 2014-02-26 2014-05-21 南通优尼科化工有限公司 Ethylenediamine tetramethylenephosphonic acid (EDTMP) scale inhibitor
CN106164211A (en) * 2013-09-24 2016-11-23 阿肯马法国公司 There is the anticorrosive preparaton of storage stability
CN109158214A (en) * 2018-06-29 2019-01-08 昆明理工大学 A kind of floatation separation process of copper sulfide zinc ore

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100460564C (en) * 2005-10-31 2009-02-11 中国石油化工股份有限公司 Method for restraining corrosion by circulating cooling water of containing sulphur
CN102718329A (en) * 2012-06-28 2012-10-10 山东省泰和水处理有限公司 Composite corrosion inhibition antisludging agent for ultralow rigidity circulation cooling water and preparation method thereof
CN106164211A (en) * 2013-09-24 2016-11-23 阿肯马法国公司 There is the anticorrosive preparaton of storage stability
CN106164211B (en) * 2013-09-24 2022-06-24 阿肯马法国公司 Anti-corrosion formulations with storage stability
CN103803731A (en) * 2014-02-26 2014-05-21 南通优尼科化工有限公司 Ethylenediamine tetramethylenephosphonic acid (EDTMP) scale inhibitor
CN109158214A (en) * 2018-06-29 2019-01-08 昆明理工大学 A kind of floatation separation process of copper sulfide zinc ore

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