JP6357817B2 - Method for preventing zinc-based scale and zinc-based scale inhibitor - Google Patents
Method for preventing zinc-based scale and zinc-based scale inhibitor Download PDFInfo
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- JP6357817B2 JP6357817B2 JP2014052063A JP2014052063A JP6357817B2 JP 6357817 B2 JP6357817 B2 JP 6357817B2 JP 2014052063 A JP2014052063 A JP 2014052063A JP 2014052063 A JP2014052063 A JP 2014052063A JP 6357817 B2 JP6357817 B2 JP 6357817B2
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims description 54
- 239000011701 zinc Substances 0.000 title claims description 54
- 229910052725 zinc Inorganic materials 0.000 title claims description 54
- 238000000034 method Methods 0.000 title claims description 13
- 230000003405 preventing effect Effects 0.000 title claims description 12
- 239000002455 scale inhibitor Substances 0.000 title claims description 10
- 150000003839 salts Chemical class 0.000 claims description 53
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 230000002265 prevention Effects 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 38
- 230000000694 effects Effects 0.000 description 11
- 239000003814 drug Substances 0.000 description 9
- 229940079593 drug Drugs 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000008234 soft water Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229940120146 EDTMP Drugs 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229940123973 Oxygen scavenger Drugs 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000004110 Zinc silicate Substances 0.000 description 1
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001370 alpha-amino acid derivatives Chemical class 0.000 description 1
- 235000008206 alpha-amino acids Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- DHGWZWRJBUSWOV-UHFFFAOYSA-L dichlorozinc dihydrate Chemical compound O.O.[Cl-].[Cl-].[Zn+2] DHGWZWRJBUSWOV-UHFFFAOYSA-L 0.000 description 1
- BXLLINKJZLDGOX-UHFFFAOYSA-N dimethoxyphosphorylmethanamine Chemical compound COP(=O)(CN)OC BXLLINKJZLDGOX-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- -1 polysiloxane Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 1
- 235000019352 zinc silicate Nutrition 0.000 description 1
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- Preventing Corrosion Or Incrustation Of Metals (AREA)
Description
本発明は、ボイラ水系システム等において生じる亜鉛系スケールの防止方法と亜鉛系スケール防止剤に関する。 The present invention relates to a method for preventing a zinc-based scale generated in a boiler water system and the like and a zinc-based scale inhibitor.
近年、エネルギーコストを削減するため、系外にブローされる水の量を減らして、高濃度で運転する水系システムが増加している。このような水系システムでは、水中のカルシウム、マグネシウム及びシリカなどのスケール成分も高濃度となるため、これらの成分がスケール化して析出することにより、熱交換器の熱効率の低下や配管の閉塞などを引き起こすことがある。また各種水系には、防食を目的に使用されている亜鉛めっき鋼管（白ガス管）があり、水中に亜鉛イオンが溶出することで、同様にスケール化による障害が発生することがある。 In recent years, in order to reduce energy costs, the number of water systems that operate at a high concentration by reducing the amount of water blown out of the system is increasing. In such an aqueous system, scale components such as calcium, magnesium, and silica in the water also have a high concentration. Therefore, these components are scaled and deposited, thereby reducing the heat efficiency of the heat exchanger and blocking the piping. May cause. In addition, various water systems include galvanized steel pipes (white gas pipes) used for the purpose of anticorrosion, and zinc ions may elute into the water, which may similarly cause obstacles due to scaling.
特に、ボイラ水系では、ボイラ缶内に持ち込まれたカルシウム、マグネシウム、シリカ、鉄及び亜鉛などのスケール成分は、熱負荷の高い伝熱面でスケール化して付着するため、鋼材の過熱による膨張、湾曲、破裂や熱効率の低下を引き起こす原因となる。また、伝熱面へのスケールの付着は、伝熱阻害を引き起こし、エネルギーロスが生じるため、燃料費の増加にもつながる。
中でも、亜鉛成分は、給水中のケイ酸と結合し、ケイ酸亜鉛、塩基性炭酸亜鉛、水酸化亜鉛等の亜鉛系スケールを発生させる。
In particular, in boiler water systems, scale components such as calcium, magnesium, silica, iron, and zinc brought into the boiler can scale and adhere on the heat transfer surface with high heat load. , Causing rupture and reduced thermal efficiency. In addition, adhesion of the scale to the heat transfer surface causes heat transfer inhibition and energy loss, leading to an increase in fuel cost.
Especially, a zinc component couple | bonds with the silicic acid in feed water, and generates zinc scales, such as zinc silicate, basic zinc carbonate, and zinc hydroxide.
従来、ボイラ水系などの亜鉛系スケールを防止する方法として、種々の提案がなされており、このうち、特許文献１には、アクリル酸系重合体又はその水溶性塩と、ホスホン酸、α−アミノカルボン酸又はそれらの水溶性塩からなる化合物を含む亜鉛スケール分散剤を添加することにより、缶内に持ち込まれた給水中の亜鉛系スケール成分の系内への付着を抑制すると共に、ブローよってこれらの成分を系外に排出する水処理方法が提案されている。 Conventionally, various proposals have been made as methods for preventing zinc-based scales such as boiler water systems. Among these, Patent Document 1 discloses an acrylic acid polymer or a water-soluble salt thereof, phosphonic acid, α-amino acid. By adding a zinc scale dispersant containing a compound comprising a carboxylic acid or a water-soluble salt thereof, the adhesion of zinc-based scale components in the feed water brought into the can to the system is suppressed, and these are blown by blowing. A water treatment method has been proposed in which the components are discharged out of the system.
しかしながら、特許文献１で提案されている薬剤を、所定の添加量で添加しても、実機の小型貫流ボイラにおいては、亜鉛系スケールの防止効果が不十分であった。 However, even if the chemical proposed in Patent Document 1 is added in a predetermined addition amount, the effect of preventing the zinc-based scale is insufficient in the actual small-sized once-through boiler.
本発明は、上記した従来の問題点を改善し、ボイラ水系システム等において、亜鉛系スケールを効果的に防止する亜鉛系スケールの防止方法及び亜鉛系スケール防止剤を提供することを課題とする。 An object of the present invention is to provide a zinc-based scale prevention method and a zinc-based scale inhibitor that effectively improve the above-described conventional problems and effectively prevent zinc-based scale in a boiler aqueous system and the like.
本発明者らは、上記課題を解決すべく鋭意検討を重ねた結果、ホスホン酸及び／又はその塩の中でも、特に２−ヒドロキシエチル−１,２−ジホスホン酸及び／又はその塩を用い、これと特定の分子量のポリメタクリル酸及び／又はその塩を併用することにより、従来よりも格段に高い亜鉛系スケール防止効果を得ることができることを見出した。 As a result of intensive studies to solve the above problems, the present inventors have used 2-hydroxyethyl-1,2-diphosphonic acid and / or a salt thereof, among phosphonic acid and / or a salt thereof. And the use of polymethacrylic acid having a specific molecular weight and / or a salt thereof together, it has been found that a significantly higher zinc-based scale preventing effect can be obtained.
本発明はこのような知見に基づいて達成されたものであり、以下を要旨とする。 The present invention has been achieved based on such findings, and the gist thereof is as follows.
［１］ 水系の亜鉛系スケールを防止する方法であって、該水系に、２−ヒドロキシエチル−１,２−ジホスホン酸及び／又はその塩と、重量平均分子量１，０００〜１００，０００のポリメタクリル酸及び／又はその塩を添加することを特徴とする亜鉛系スケールの防止方法。 [1] A method for preventing an aqueous zinc-based scale, wherein the aqueous system includes 2-hydroxyethyl-1,2-diphosphonic acid and / or a salt thereof and a polysiloxane having a weight average molecular weight of 1,000 to 100,000. A method for preventing a zinc-based scale, comprising adding methacrylic acid and / or a salt thereof.
［２］ ２−ヒドロキシエチル−１,２−ジホスホン酸及び／又はその塩を水系の濃度が０．１〜１，０００ｍｇ／Ｌとなるように添加すると共に、ポリメタクリル酸及び／又はその塩を水系の濃度が０．１〜５００ｍｇ／Ｌとなるように添加することを特徴とする［１］に記載の亜鉛系スケールの防止方法。 [2] 2-hydroxyethyl-1,2-diphosphonic acid and / or a salt thereof are added so that the aqueous concentration is 0.1 to 1,000 mg / L, and polymethacrylic acid and / or a salt thereof is added. The method for preventing a zinc-based scale according to [1], wherein the aqueous-based concentration is 0.1 to 500 mg / L.
［３］ 前記水系がボイラ水系であることを特徴とする［１］又は［２］に記載の亜鉛系スケールの防止方法。 [3] The method for preventing a zinc-based scale according to [1] or [2], wherein the aqueous system is a boiler aqueous system.
［４］ ２−ヒドロキシエチル−１,２−ジホスホン酸及び／又はその塩と、重量平均分子量１，０００〜１００，０００のポリメタクリル酸及び／又はその塩を含むことを特徴とする水系の亜鉛系スケール防止剤。 [4] Aqueous zinc comprising 2-hydroxyethyl-1,2-diphosphonic acid and / or a salt thereof and polymethacrylic acid having a weight average molecular weight of 1,000 to 100,000 and / or a salt thereof. System scale inhibitor.
［５］ ２−ヒドロキシエチル−１,２−ジホスホン酸及び／又はその塩と、ポリメタクリル酸及び／又はその塩とを、２−ヒドロキシエチル−１,２−ジホスホン酸及び／又はその塩：ポリメタクリル酸及び／又はその塩＝１：０．０１〜１：１００（重量比）の割合で含むことを特徴とする［４］に記載の水系の亜鉛系スケール防止剤。 [5] 2-hydroxyethyl-1,2-diphosphonic acid and / or a salt thereof and polymethacrylic acid and / or a salt thereof are converted into 2-hydroxyethyl-1,2-diphosphonic acid and / or a salt thereof: poly Methacrylic acid and / or a salt thereof = 1: 0.01-1: 100 (weight ratio). The aqueous zinc-based scale inhibitor as set forth in [4] .
本発明によれば、小型貫流ボイラ等、各種の蒸気発生システムにおいて、２−ヒドロキシエチル−１,２−ジホスホン酸及び／又はその塩によるキレート効果と、ポリメタクリル酸及び／又はその塩による分散効果で、亜鉛系スケール成分を効果的にブロー水中に排出し、缶内への亜鉛系スケールの付着を高度に防止することができる。 According to the present invention, in various steam generation systems such as a small once-through boiler, a chelating effect by 2-hydroxyethyl-1,2-diphosphonic acid and / or a salt thereof and a dispersing effect by polymethacrylic acid and / or a salt thereof. Thus, the zinc-based scale component can be effectively discharged into the blow water, and the adhesion of the zinc-based scale to the can can be highly prevented.
以下に本発明の実施の形態を詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
本発明においては、ボイラ水系等の亜鉛系スケールの析出の問題がある水系に、２−ヒドロキシエチル−１,２−ジホスホン酸及び／又はその塩と、重量平均分子量１，０００〜１００，０００のポリメタクリル酸及び／又はその塩とを添加する。
なお、２−ヒドロキシエチル−１,２−ジホスホン酸塩としては、２−ヒドロキシエチル−１,２−ジホスホン酸のナトリウム塩、カリウム塩、アンモニウム塩を用いることができる。ポリメタクリル酸塩としてはポリメタクリル酸のナトリウム塩、カリウム塩、アンモニウム塩を用いることができる。
In the present invention, 2-hydroxyethyl-1,2-diphosphonic acid and / or a salt thereof and a weight average molecular weight of 1,000 to 100,000 are added to an aqueous system having a problem of precipitation of zinc-based scale such as a boiler aqueous system. Polymethacrylic acid and / or its salt is added.
In addition, as 2-hydroxyethyl-1,2-diphosphonate, sodium salt, potassium salt, and ammonium salt of 2-hydroxyethyl-1,2-diphosphonic acid can be used. As polymethacrylate, sodium salt, potassium salt, and ammonium salt of polymethacrylic acid can be used.
ポリメタクリル酸及び／又はその塩の重量平均分子量は１，０００〜１００，０００であり、好ましくは１，０００〜５０，０００である。ポリメタクリル酸及び／又はその塩の重量平均分子量が上記範囲であると、亜鉛系スケールに対する分散効果に優れたものとなり、好ましい。 The weight average molecular weight of polymethacrylic acid and / or a salt thereof is 1,000 to 100,000, preferably 1,000 to 50,000. When the weight average molecular weight of polymethacrylic acid and / or a salt thereof is in the above range, the dispersion effect on the zinc-based scale is excellent, which is preferable.
水系への２−ヒドロキシエチル−１,２−ジホスホン酸及び／又はその塩の添加量は、処理対象水系の水質（亜鉛濃度）、亜鉛系スケールの析出傾向によっても異なるが、水系の２−ヒドロキシエチル−１,２−ジホスホン酸及び／又はその塩の濃度が、２−ヒドロキシエチル−１，２−ジホスホン酸として重量比で、水中の亜鉛濃度に対して４倍以上、好ましくは６倍以上、より好ましくは８倍以上の濃度となるように添加するのが良く、０．１〜１，０００ｍｇ／Ｌ、特に１〜５００ｍｇ／Ｌとなるような量とすることが好ましい。２−ヒドロキシエチル−１,２−ジホスホン酸及び／又はその塩の添加濃度が上記下限未満では十分な添加効果が得られず、上記上限を超えると、薬剤コストの面で不経済であると共に、水中のＣＯＤが上昇し、排水処理の面で好ましくない。 The amount of 2-hydroxyethyl-1,2-diphosphonic acid and / or its salt added to the aqueous system varies depending on the water quality (zinc concentration) of the aqueous system to be treated and the precipitation tendency of the zinc-based scale. The concentration of ethyl-1,2-diphosphonic acid and / or a salt thereof as a weight ratio of 2-hydroxyethyl-1,2-diphosphonic acid is not less than 4 times, preferably not less than 6 times the zinc concentration in water. More preferably, it should be added so that the concentration is 8 times or more, and it is preferably 0.1 to 1,000 mg / L, particularly 1 to 500 mg / L. If the addition concentration of 2-hydroxyethyl-1,2-diphosphonic acid and / or its salt is less than the above lower limit, a sufficient addition effect cannot be obtained, and if it exceeds the above upper limit, it is uneconomical in terms of drug cost, Underwater COD increases, which is not preferable in terms of wastewater treatment.
また、水系へのポリメタクリル酸及び／又はその塩の添加量は、処理対象水系の水質（亜鉛濃度）、亜鉛系スケールの析出傾向によっても異なるが、水系のポリメタクリル酸及び／又はその塩の濃度が０．１〜５００ｍｇ／Ｌ、特に１〜２００ｍｇ／Ｌとなるような量とすることが好ましい。ポリメタクリル酸及び／又はその塩の添加濃度が上記下限未満では、十分な添加効果が得られず、上記上限を超えてもそれに見合う効果の向上は得られず、薬剤コストの面で不経済であると共に、水中のＣＯＤが上昇し、排水処理の面で好ましくない。 The amount of polymethacrylic acid and / or its salt added to the aqueous system varies depending on the water quality (zinc concentration) of the aqueous system to be treated and the precipitation tendency of the zinc-based scale. It is preferable that the concentration be 0.1 to 500 mg / L, particularly 1 to 200 mg / L. If the addition concentration of polymethacrylic acid and / or its salt is less than the above lower limit, a sufficient addition effect cannot be obtained, and even if it exceeds the upper limit, an improvement in the effect corresponding to it cannot be obtained, which is uneconomical in terms of drug cost In addition, the COD in water increases, which is not preferable in terms of wastewater treatment.
２−ヒドロキシエチル−１,２−ジホスホン酸及び／又はその塩とポリメタクリル酸及び／又はその塩との添加量比には特に制限はないが、水系の２−ヒドロキシエチル−１,２−ジホスホン酸及び／又はその塩とポリメタクリル酸及び／又はその塩の濃度比が重量比で２−ヒドロキシエチル−１,２−ジホスホン酸及び／又はその塩：ポリメタクリル酸及び／又はその塩＝１：０．０１〜１：１００、特に１：０．０１〜１：１０の範囲となるように添加することが、両者の併用による効果を得る上で好ましい。
従って、２−ヒドロキシエチル−１,２−ジホスホン酸及び／又はその塩とポリメタクリル酸及び／又はその塩とを含む本発明の亜鉛系スケール防止剤は、上記のような割合で２−ヒドロキシエチル−１,２−ジホスホン酸及び／又はその塩とポリメタクリル酸及び／又はその塩とを含むものであることが好ましい。
There is no particular limitation on the ratio of the addition amount of 2-hydroxyethyl-1,2-diphosphonic acid and / or salt thereof to polymethacrylic acid and / or salt thereof, but aqueous 2-hydroxyethyl-1,2-diphosphone is not limited. The concentration ratio of acid and / or salt thereof to polymethacrylic acid and / or salt thereof is 2-hydroxyethyl-1,2-diphosphonic acid and / or salt thereof by weight ratio: polymethacrylic acid and / or salt thereof = 1. It is preferable to add so that it may become the range of 0.01-1: 100, especially 1: 0.01-1: 10, when obtaining the effect by combined use of both.
Therefore, the zinc-based scale inhibitor of the present invention containing 2-hydroxyethyl-1,2-diphosphonic acid and / or a salt thereof and polymethacrylic acid and / or a salt thereof is 2-hydroxyethyl in the above proportion. It is preferable that 1,2-diphosphonic acid and / or its salt and polymethacrylic acid and / or its salt are included.
なお、本発明において、２−ヒドロキシエチル−１,２−ジホスホン酸及び／又はその塩とポリメタクリル酸及び／又はその塩とは予め混合して添加してもよく、各々別々に添加してもよい。予め混合して添加する場合、これらを水溶液として添加してもよい。従って、本発明の亜鉛系スケール防止剤は、２−ヒドロキシエチル−１,２−ジホスホン酸及び／又はその塩とポリメタクリル酸及び／又はその塩とを含む水溶液であってもよく、これらが別々に提供されるものであってもよい。 In the present invention, 2-hydroxyethyl-1,2-diphosphonic acid and / or a salt thereof and polymethacrylic acid and / or a salt thereof may be mixed in advance or added separately. Good. When mixing and adding in advance, these may be added as an aqueous solution. Therefore, the zinc-based scale inhibitor of the present invention may be an aqueous solution containing 2-hydroxyethyl-1,2-diphosphonic acid and / or a salt thereof and polymethacrylic acid and / or a salt thereof. May be provided.
本発明の対象水系としては、ボイラ水系が挙げられるが、他にも水中に亜鉛が存在し、亜鉛系スケールが問題となる系であればいかなる系であっても使用可能である。
このような対象水系に供給する水（給水）としては、逆浸透膜処理水等の脱塩水、軟水、イオン交換水などが挙げられる。
The target water system of the present invention includes a boiler water system, but any system can be used as long as zinc is present in the water and the zinc-based scale is a problem.
Examples of water (water supply) supplied to the target water system include desalted water such as reverse osmosis membrane treated water, soft water, and ion exchange water.
また、これらの水系には、炭酸ナトリウム、炭酸水素ナトリウム、水酸化カリウム、水酸化ナトリウム等のアルカリ剤を添加してｐＨ調整してもよい。この調整ｐＨ値としてはボイラ水系では１０．５〜１２．０程度が好ましい。 Moreover, you may adjust pH by adding alkaline agents, such as sodium carbonate, sodium hydrogencarbonate, potassium hydroxide, sodium hydroxide, to these aqueous systems. The adjusted pH value is preferably about 10.5 to 12.0 in a boiler water system.
更に、本発明においては、上記アルカリ剤の他に、２−ヒドロキシエチル−１,２−ジホスホン酸及び／又はその塩及びポリメタクリル酸及び／又はその塩と共に、公知のスケール分散剤、防食剤、脱酸素剤、揮発性アミン等の他の薬剤を本発明の目的を妨げない範囲で任意に添加してもよい。これらの他の薬剤は、２−ヒドロキシエチル−１,２−ジホスホン酸及び／又はその塩及びポリメタクリル酸及び／又はその塩と共に添加してもよく、別々に添加してもよい。従って、本発明の亜鉛系スケール防止剤は、これらの薬剤を更に含有するものであってもよく、その際に、他の薬剤が混合されたものであってもよく、別々に供給されるものであってもよい。 Further, in the present invention, in addition to the above alkaline agent, together with 2-hydroxyethyl-1,2-diphosphonic acid and / or a salt thereof and polymethacrylic acid and / or a salt thereof, a known scale dispersant, anticorrosive agent, Other agents such as oxygen scavengers and volatile amines may be optionally added as long as the object of the present invention is not impaired. These other agents may be added together with 2-hydroxyethyl-1,2-diphosphonic acid and / or its salt and polymethacrylic acid and / or its salt, or may be added separately. Therefore, the zinc-based scale inhibitor of the present invention may further contain these agents, and in that case, other agents may be mixed and supplied separately. It may be.
以下に実施例を挙げて本発明をより具体的に説明する。 Hereinafter, the present invention will be described more specifically with reference to examples.
なお、以下の実施例及び比較例で用いた薬剤の詳細は、以下の通りである。
＜ポリマー系薬剤＞
ＰＭＡＡ：ポリメタクリル酸 重量平均分子量１０，０００
ＰＡＡ：ポリアクリル酸 重量平均分子量２１，０００
ＡＡ−ＡＭＰＳ：アクリル酸（ＡＡ）と２−アクリルアミド−２−メチルプロパンス
ルホン酸（ＡＭＰＳ）とのコポリマー
ＡＡ：ＡＭＰＳ＝８０：２０（モル比）
重量平均分子量１１，０００
ＡＡ−ＨＡＰＳ：アクリル酸（ＡＡ）と３−アリルオキシ−２−ヒドロキシ−１−プ
ロパンスルホン酸（ＨＡＰＳ）とのコポリマー
ＡＡ：ＨＡＰＳ＝８０：２０（モル比）
重量平均分子量１０，０００
＜ホスホン酸系薬剤＞
ＨＥＤＰ：２−ヒドロキシエチル−１,２−ジホスホン酸
ＥＮＴＭＰ：エチレンジアミンテトラメチレンホスホン酸
ＡＴＭＰ：アミノトリメチルホスホン酸
The details of the drugs used in the following Examples and Comparative Examples are as follows.
<Polymer drugs>
PMAA: polymethacrylic acid weight average molecular weight 10,000
PAA: polyacrylic acid weight average molecular weight 21,000
AA-AMPS: Acrylic acid (AA) and 2-acrylamido-2-methylpropanes
Copolymer with sulfonic acid (AMPS)
AA: AMPS = 80: 20 (molar ratio)
Weight average molecular weight 11,000
AA-HAPS: acrylic acid (AA) and 3-allyloxy-2-hydroxy-1-propyl
Copolymer with lopansulfonic acid (HAPS)
AA: HAPS = 80: 20 (molar ratio)
Weight average molecular weight 10,000
<Phosphonic acid drugs>
HEDP: 2-hydroxyethyl-1,2-diphosphonic acid ENTMP: ethylenediaminetetramethylenephosphonic acid ATMP: aminotrimethylphosphonic acid
［実施例１，２、比較例１〜１０］
下記の条件で、亜鉛スケール防止効果を調べる試験を行った。
即ち、以下の小型貫流ボイラを用いて、亜鉛めっき配管等から亜鉛イオンが給水中に混入した場合を想定した以下の条件で、ボイラ伝熱面に亜鉛スケールが付着せず、ブロー水中に亜鉛が排出されるか否かの効果を確認した。
試験装置 ：実験用小型貫流ボイラ
給水 ：軟水（塩化物イオン２０ｍｇ／Ｌ、硫酸イオン２０ｍｇ／Ｌ、シリカ３０
ｍｇ／Ｌ、Ｍアルカリ２０ｍｇ−ＣａＣＯ３／Ｌ）に、塩化亜鉛２水和物
を添加して、亜鉛濃度１０ｍｇ／Ｌとなるように調製した水
薬剤 ：表１記載のポリマー系薬剤とホスホン酸系薬剤をそれぞれの濃度で用いた （ただし、比較例１では薬剤添加せず）。
ボイラ水ｐＨ：１１．５となるように水酸化ナトリウムを用いて調整した。
給水温度 ：２５℃
運転圧力 ：０．７ＭＰａ
給水量 ：４５０Ｌ／ｈｒ
濃縮倍数 ：１０倍
試験期間 ：６６時間
[Examples 1 and 2 and Comparative Examples 1 to 10]
The test which investigates a zinc scale prevention effect was done on the following conditions.
In other words, using the following small once-through boiler, zinc scale does not adhere to the boiler heat transfer surface, and zinc does not adhere to the blow water under the following conditions assuming that zinc ions are mixed into the feed water from galvanized piping or the like. The effect of whether or not it was discharged was confirmed.
Test apparatus: Experimental small once-through boiler Water supply: Soft water (chloride ion 20 mg / L, sulfate ion 20 mg / L, silica 30
mg / L, M alkali 20 mg-CaCO 3 / L), zinc chloride dihydrate
The water was prepared to have a zinc concentration of 10 mg / L. Drug: The polymer drug and the phosphonic acid drug listed in Table 1 were used at their respective concentrations (however, in Comparative Example 1, no drug was added). .
The boiler water pH was adjusted to 11.5 using sodium hydroxide.
Water supply temperature: 25 ° C
Operating pressure: 0.7 MPa
Water supply amount: 450L / hr
Concentration multiple: 10 times Test period: 66 hours
ボイラの給水ラインに、表１に示す薬剤を表１に示す濃度となるように添加しながら、ボイラを６６時間運転した。
試験中、薬注点後の給水とブロー水を数回サンプリングし、亜鉛濃度（ｍｇ／Ｌ）を分析した後、下記式より亜鉛排出率を求めた。
亜鉛排出率（％）＝ブロー水亜鉛濃度÷（給水亜鉛濃度×濃縮倍数）×１００
また、試験前、ボイラ缶内に鋼材製テストピース（ＳＧＰ、３０×５０×１０ｍｍ、＃４００研磨）を設置し、試験後、テストピースを取り出し、試験前後の重量から亜鉛スケール付着量を求めた。
これらの結果を表１に示す。
The boiler was operated for 66 hours while adding the chemicals shown in Table 1 to the boiler water supply line so as to have the concentrations shown in Table 1.
During the test, the feed water and blow water after the chemical injection point were sampled several times, and after analyzing the zinc concentration (mg / L), the zinc discharge rate was determined from the following formula.
Zinc emission rate (%) = blow water zinc concentration ÷ (feed water zinc concentration x concentration factor) x 100
Further, before the test, a steel test piece (SGP, 30 × 50 × 10 mm, # 400 polishing) was placed in the boiler can, and after the test, the test piece was taken out and the zinc scale adhesion amount was determined from the weight before and after the test. .
These results are shown in Table 1.
実施例１、２に示す通り、ＨＥＤＰとＰＭＡＡを併用することで亜鉛の排出量が上がり、缶内への亜鉛スケールの付着を優れた効果で防止することができることが確認された。 As shown in Examples 1 and 2, it was confirmed that the combined use of HEDP and PMAA increases the amount of zinc discharged and can prevent the zinc scale from adhering to the inside of the can with an excellent effect.
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