CN1557746A - Corrosion inhibitor for steam condensate system of industrial boiler and process for manufacturing same - Google Patents

Corrosion inhibitor for steam condensate system of industrial boiler and process for manufacturing same Download PDF

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Publication number
CN1557746A
CN1557746A CNA2004100031415A CN200410003141A CN1557746A CN 1557746 A CN1557746 A CN 1557746A CN A2004100031415 A CNA2004100031415 A CN A2004100031415A CN 200410003141 A CN200410003141 A CN 200410003141A CN 1557746 A CN1557746 A CN 1557746A
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alkylamine
carbon atoms
industrial boiler
fatty acid
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张文利
张晓丽
魏刚
陶月明
袁适安
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Abstract

The corrosion inhibitor for industrial boiler steam condensating water system includes alkyl amine with 12-18 carbon atoms or epoxy alkyl amine, Tween-60, Span-60, morpholine, cyclohexylamine and/or ammonia, and water. The corrosion inhibitor is emulsified liquid, and has functions of filming and neutralizing, reasonable steam-liquid distribution ratio, lower consumption, concentration indication, corrosion inhibiting efficiency over 98 %, obvious energy saving function and simple use, and may be used widely in various industrial boiler steam condensating water systems.

Description

Industrial Boiler steam condenses system inhibiter and manufacture method thereof
Technical field
The present invention relates to the boiler water processing technical field, particularly relate to Industrial Boiler steam condenses system inhibiter and manufacture method thereof.
Background technology
Steam condenses particularly Boiler Steam condensed water is the high-quality oiler feed that contains heat energy, and the recovered steam condensed water is boiler water saving, energy-conservation effective measures.The heat that contains in the condensed water can reach 20%~30% of steam total heat, is used as recovery, can obviously reduce boiler oil consumption, reduces the softening water consumption, reduces the production of steam cost, improves the boiler water quality situation.Because the improvement of boiler water quality situation can also significantly reduce the heat-energy losses that draining of boiler and blowdown cause, improve boiler efficiency, make boiler operatiopn safer.But; owing to contain aerobic and free carbon dioxide in the steam; after heat exchange during vapor condensation; carbonic acid gas is dissolved in and forms carbonic acid in the condensed water; thereby destroy the protective membrane of metallic surface and cause acid attack; corrosion of metal speed depends on temperature and acid concentration, and the corrosion speed of carbon steel in condensed water is directly proportional with carbonate concentration when pH<6.2.When the pH of condensed water hanged down, the corrosion product dissolving caused condensed water to be polluted by iron ion.Undressed condensed water is during as boiler water-filling, and contained a large amount of iron ions can cause bigger harm at boiler heat-transfer face generation secondary fouling and underdeposit corrosion in the water, and making steam condenses directly recycle has certain degree of difficulty.Therefore, have a lot of Industrial Boilers to design, just do not consider when installing the recovery of condensed water in system and steam plant, the steam condenses that quality is good drains into trench and wastes.Though some user reclaims condensed water and does oiler feed, owing to lack effective pipeline corrosion protection measure and condensed water treatment technology, condensate return pipe road seriously corroded, iron ion content is higher in the condensed water, directly influences the safe operation of boiler.Existing deironing measure mainly is the aeration filtration deironing, iron concentration reduces in the condensed water though can make, and pollutes still to exist, and corrosion still takes place, general condensing water conduit can cause the riddled with gaping wounds situation that can't repair of condensing water conduit because of leaking appears in corrosion failure in two, three years.And the problem that this method exists is that investment is big, floor space is big, and can not thoroughly prevent the corrosion of condensing water conduit.Industrial Boiler condensed water recovery utilization rate up to standard is less than 20% at present.
China's active boiler reaches more than 50 ten thousand at present, produces steam tons up to a million every day.Country for the such serious water shortage of China, energy shortage, ecological environment frailty realizes the abundant recycling of condensed water, and its water saving, save energy and protection environment produce huge social benefit and direct economic benefit.
Summary of the invention
The objective of the invention is to overcome the problem that above-mentioned Industrial Boiler condensed water exists, be engaged in the Industrial Boiler water for a long time through the contriver, especially a kind of easy, stable, Industrial Boiler steam condenses system inhibiter is efficiently developed in the exploitation of Industrial Boiler vapor condenses water treatment, research and practice accumulation.
Another purpose of the present invention provides a kind of manufacture method of Industrial Boiler steam condenses system inhibiter.
Industrial Boiler steam condenses system inhibiter provided by the invention comprises alkylamine or its epoxidized alkyl amine of 12-18 carbon atom of 10-100 weight part, 0.01-0.03 weight part polyoxyethylene sorbitan fatty acid ester (trade name is a tween), 0.001-0.005 weight part sorbitan fatty acid ester (trade name is this Pan), 0-500 weight part Lin, 70-400 weight part hexahydroaniline and/or ammonia, and suitable quantity of water.Preferably include alkylamine or its epoxidized alkyl amine of 12-18 carbon atom of 15-70 weight part, 0.01-0.02 weight part polyoxyethylene sorbitan fatty acid ester, 0.0015-0.004 weight part sorbitan fatty acid ester, 100-300 weight part Lin, 100-350 weight part hexahydroaniline and/or ammonia, suitable quantity of water.The alkylamine or its epoxidized alkyl amine that more preferably comprise 12-18 carbon atom of 20-50 weight part, 0.015-0.02 weight part polyoxyethylene sorbitan fatty acid ester, 0.002-0.003 weight part sorbitan fatty acid ester, 100-200 weight part Lin, 150-300 weight part hexahydroaniline and/or ammonia, suitable quantity of water.
In the Industrial Boiler steam condenses system inhibiter provided by the invention, the alkylamine of a described 12-18 carbon atom is straight chain amine, chain amine, first amine (primary amine), second amine (secondary amine), triamine (tertiary amine), for example lauryl amine, tridecyl amine, tetradecylamine, pentadecyl amine, hexadecylamine, heptadecyl amine, octadecylamine, 3-methyl-6-propyl group-octylame, 4-ethyl-6-propyl group-nonyl amine, 2-ethyl-5-propyl group-decyl amine, 3-ethyl-6-butyl heptadecyl-amine, Tributylamine ((CH 3CH 2CH 2CH 2) 3N), three the eleventh of the twelve Earthly Branches amine, trihexylamine, dihexylamine, Di-Octyl amine, heptadecane diamines, octadecamethylene diamine etc., be preferably alkylamine or its epoxidized alkyl amine of 16-18 carbon atom, for example cetylamine, n-Hexadecane diamines, heptadecylamine (HDA), octadecane amine, Di-Octyl amine, 3-ethyl-6-butyl heptadecyl-amine, trihexylamine 4-ethyl-6-amyl group-decyl amine,, 3-ethyl-6-butyl heptadecyl-amine etc.These amine can use or mix use separately, mix and use than not being strict with, can be in any ratio, and general consumption is the 10-100 weight part in inhibiter provided by the invention, is preferably the 10-70 weight part, more preferably the 20-50 weight part.
Described epoxidized alkyl amine is meant alkylamine and the oxyethane or the propylene oxide of 12-18 carbon atom, preferably carries out the product of epoxidation reaction with oxyethane, for example
R-NH-CH 2-CH 2(CH 2CH 2O) N-2-OCH 2CH 2OH and
Figure A20041000314100061
The end reaction thing is actually homologue and isomer mixture, and the alkylamine of an above-mentioned 12-18 carbon atom or its epoxidized alkyl amine all can commercially availablely obtain.Amino (NH in these alkylamines 2) in metallic surface absorption, forming unimolecular layer protective membrane with hydrophobic effect, protective membrane is isolated metallic surface and water; Because the void ratio O between membrane molecule 2And CO 2The cross section little, thereby prevented O 2And CO 2To corrosion of metal, protective membrane is fine and close and stable.
Described polyoxyethylene sorbitan fatty acid ester is meant that trade name is the various polyoxyethylene sorbitan fatty acid esters (abbreviating tween down as) of tween, kind and formed oxyethane number according to used lipid acid, and different varieties is arranged, mono laurate for example, oxyethane number are called polysorbas20 during for 21-22; Single palmitinic acid, oxyethane number are called polysorbate40 during for 18-22; Stearinsaeure, oxyethane number are called polysorbate60 during for 18-22; Single oleic acid, oxyethane number are called tween 80 during for 21-26; Three oleic acid, oxyethane number are to be called polysorbate85 or the like at 22 o'clock; Also has tween 61 (polyoxyethylene (4) sorbitan monostearate), sorbimacrogol oleate100 (polyoxyethylene (5) sorbitan monooleate), tween 21 (polyoxyethylene (4) sorbitan mono-laurate) etc.Be preferably polysorbate60-85, polysorbate60 for example, tween 61, tween 80, sorbimacrogol oleate100, polysorbate85.These polyoxyethylene sorbitan fatty acid esters consumption in inhibiter is the 0.01-0.03 weight part, is preferably the 0.01-0.02 weight part, more preferably the 0.015-0.02 weight part.Described sorbitan fatty acid ester is meant that trade name is this Pan's various sorbitan fatty acid esters, according to used lipid acid kind difference various different varietiess are arranged, this Pan 20 (sorbitan mono-laurate) for example, this Pan 40 (anhydrous sorbitol list palmitinic acid acid esters), this Pan 60 (sorbitan monostearate), this Pan 65 (anhydrous sorbitol tristearate), this Pan 80 (sorbitan monooleate), this Pan 85 (Witconol AL 69-66) etc., be preferably this Pan 40-80, this Pan 40,60,65 for example, 80 etc., these sorbitan fatty acid esters consumption in inhibiter is the 0.001-0.005 weight part, is preferably 0.0015-0.004, more preferably the 0.002-0.003 weight part.
Described hexahydroaniline and/or ammonia can use or mix use separately separately, mix not strict demand of ratio of mixture when using, but arbitrary proportion.In inhibiter of the present invention, also can use and to discharge NH 3Compound, as NH 4OH etc. are not as the criterion as long as native system is not produced detrimentally affect.
Described suitable quantity of water is meant the requirement according to the user, makes the inhibiter product emulsion and has different concns, and the water that adds different amounts is to satisfy market demands.
The manufacture method of Industrial Boiler steam condenses system inhibiter provided by the invention comprises:
1, in having the container of stirring, add suitable quantity of water and be warming up to 50-55 ℃, add 0.01-0.03 weight part polyoxyethylene sorbitan fatty acid ester, 0.001-0.005 weight part sorbitan fatty acid ester, the alkylamine of 10-100 weight part 12-18 carbon atom or its epoxidized alkyl amine, stirred 5-10 minute, the homogeneous postcooling is to room temperature.
2, in reactor, add 100-400 weight part hexahydroaniline and/or ammoniacal liquor, stir, add the material that 0-300 weight part morpholine and step 1 obtain again, stir the inhibiter product that gets emulsion liquid after 2-15 minute.
Industrial Boiler steam condenses system inhibiter provided by the invention has film forming, neutralization, reasonably vapour-liquid phase partition ratio, trace add density of corrosion inhibitor deixis in inhibiter and the system.
1, film forming function:
After inhibiter adds the Industrial Boiler steam system, produce the amido (NH of so-called membrane-forming agent 2) in metallic surface absorption, forming unimolecular layer protective membrane with hydrophobic effect, this protective membrane is isolated metallic surface and water; Because " membrane-forming agent " intermolecular void ratio O 2And CO 2The cross section little, thereby prevented O 2And CO 2To corrosion of metal.Protective membrane is fine and close and stable, but for keeping it completely to need the continuous supplementation reparation.
2, in and function:
Inhibiter pH value>12 are alkalescence, have " neutralizing agent " effect and volatile, the carbonic acid in the condensed water that both neutralized, and the concentration for inhibiter in the online detection condensed water provides foundation again.
3, vapour-liquid phase function:
Inhibiter has rational vapour-liquid phase partition ratio in system's vapour-liquid in mutually, when the not enough underfilling pipeline of condensed water, and the effective vapor phase space of protect concrete water transport pipe.
4, deixis:
Because inhibiter has the properly distributed ratio in system's vapour-liquid in mutually, so vapour-liquid phase corrosion inhibitor concentration has one rationally to determine to distribute in the system, for the automatization that adds of online detection and inhibiter provides the control foundation, has guaranteed the accurate control that inhibiter adds.
Industrial Boiler steam condenses system inhibiter provided by the invention has following characteristics:
1, the emulsion bead of inhibiter carries with steam in the system, and heat exchange becomes condensed water, wherein amine (NH 2) be attracted to pipeline or container metal material surface and form protective membrane, NH 3In and CO 2, prevent acid attack, the contaminated problem of condensed water that can effectively solve condensate system corrosion and cause because of corrosion.
2, the inhibiter consumption is little in the system, is 30-50ppm.
3, condensing water temperature 70-80 ℃, directly return boiler feed water, reclaim heat, energy-saving effect is remarkable, and the expense that puts into operation is 1: 10 with energy-conservation expense ratio.
Parameter Before condensed water reclaims After condensed water reclaims
Produce steam water per ton (ton) ??1.4 ????0.2~0.3
Thermal loss of boiler blow down (%) ??20 ????5
Condensed water discharging thermosteresis (%) ??100 ????0
4, stable, be suitable for the big occasion of different operation conditions and load variations.
5, inhibiter of the present invention belongs to the source pre-treatment, the treatment process that does not allow corrosion take place, and the Industrial Boiler steam condenses is to carry out filtering type after acidic coagulation water and tube metal are corroded to handle at present.
6, be suitable for various material such as carbon steel, copper, stainless boiler condensing water conduit or interchanger etc.
7, corrosion inhibition rate is higher than 98%, and is remarkable to material corrosion mitigating effects such as steel, copper.
8, do not influence the condensed water quality, can directly return boiler feed water.
9, the iron ion content in the condensed water≤50 μ g/ liters, and the national standard oiler feed is≤300 μ g/ liters.
Industrial Boiler steam condenses system inhibiter provided by the invention is widely used in various industrial steam boilers and the condensate system below 350 ℃.
Embodiment
The present invention further specifies the present invention with the following example, protects protection scope of the present invention and is not limited to embodiment.
Embodiment 1
In having the container of stirring, add 80 ml deionized water, be heated to 55 ℃, add 0.016 gram tween 80 successively, 0.004 restrain this Pan 60, mix the back and add the straight chain alkyl amine of 16 grams, 18 carbon atoms and the straight chain alkyl amine of 4 grams, 16 carbon atoms, stir 5-10 minute homogeneous postcooling and get intermediate product to room temperature.Add 60 gram hexahydroaniline and 40 gram ammoniacal liquor (referring to ammonia weight meter) in reactor, begin to stir, add 300 gram morpholines again, stirred 1-5 minute, add above-mentioned intermediate product, restir obtained the emulsion liquid inhibiter in 3 minutes, the corrosion inhibition rate 98-99% of this inhibiter.
Embodiment 2-13
The manufacturing step of embodiment 2-13 and condition are same as embodiment 1, are not both each starting material and starting material consumption by shown in the table 1, and the gained corrosion inhibitor product is an emulsion liquid.
Table 1
Embodiment (gram)
??2 ??3 ??4 ??5 ??6 ??7 ???8 ??9 ??10 ??11 ??12 ??13
12 alkylamines ??80
12 alkylamines ??50
4-ethyl-6-propyl group nonyl amine ??30
15 alkylamines ??15
16 alkylamines ??20 ??20 ??10
Di-Octyl amine ??40 ??10
3-ethyl-6-butyl heptadecyl-amine ??40
17 alkylamines ??30
18 alkylamines ??30 ??20 ??20
Trioctylamine ??40
Polysorbas20 ??0.01 ??0.018
Polysorbate40 ??0.02 ??0.016
Polysorbate60 ??0.015 ??0.02 ??0.017
Tween 80 ??0.015 ??0.03 ??0.018
Polysorbate85 ??0.02 ??0.014
This Pan 20 ??0.004 ??0.001
This Pan 40 ??0.003 ??0.003 ??0.004
This Pan 65 ??0.004 ??0.002
This Pan 80 ??0.005 ??0.005 ??0.004
This Pan 85 ??0.003 ??0.003
Morpholine ??0 ??300 ??400 ??400 ??200 ??500 ??300 ??300 ??300 ??300 ??200
Hexahydroaniline ??200 ??100 ??100 ??300 ??200 ??300 ??20 ??150 ??200
Ammonia ??300 ??100 ??200 ??100 ??100 ??200 ??400
Suitable quantity of water ??100 ??150 ??80 ??50 ??100 ??100 ??50 ??100 ??50 ??100 ??50 ??150
Corrosion inhibition rate (%) ??98.0 ??98.8 ??99.0 ??98.7 ??98.1 ??98.0 ??98.2 ??98.8 ??98.9 ??98.5 ??98.6 ??98.8

Claims (9)

1, a kind of Industrial Boiler steam condenses system inhibiter, comprise the alkylamine of 12~18 carbon atoms of 10~100 weight parts or the alkylamine of 12~18 carbon atoms of epoxidation, 0.01~0.03 weight part polyoxyethylene sorbitan fatty acid ester, 0.001~0.005 weight part sorbitan fatty acid ester, 0~500 weight part morpholine, 70~400 weight part hexahydroaniline and/or ammonia, suitable quantity of water.
2, according to the Industrial Boiler steam condenses system inhibiter of claim 1, comprise the alkylamine of 12~18 carbon atoms of 15~70 weight parts or the alkylamine of 12~18 carbon atoms of epoxidation, 0.01~0.02 weight part polyoxyethylene sorbitan fatty acid ester, 0.0015~0.004 weight part sorbitan fatty acid ester, 100~300 weight part morpholines, 100~350 weight part hexahydroaniline and/or ammonia, suitable quantity of water.
3, according to the Industrial Boiler steam condenses system inhibiter of claim 2, comprise the alkylamine of 12~18 carbon atoms of 20~50 weight parts or the alkylamine of 12~18 carbon atoms of epoxidation, 0.015~0.02 weight part polyoxyethylene sorbitan fatty acid ester, 0.002~0.003 weight part sorbitan fatty acid ester, 100~200 weight part morpholines, 150~300 weight part hexahydroaniline and/or ammonia, suitable quantity of water.
4,, it is characterized in that described alkylamine is the alkylamine of 16~18 carbon atoms or the alkylamine of 16~18 carbon atoms of epoxidation according to each described Industrial Boiler steam condenses system inhibiter of claim 1~3.
5,, it is characterized in that the alkylamine of described 12~18 carbon atoms or the alkylamine of 12~18 carbon atoms of epoxidation are cetylamine, heptadecylamine (HDA), octadecane amine according to each described Industrial Boiler steam condenses system inhibiter of claim 1~3.4-ethyl-6-amyl group-decyl amine, 3-ethyl-6-butyl heptadecyl-amine, trihexylamine or Di-Octyl amine or 3-ethyl-6-propyl group tridecyl amine and oxyethane alkylamine thereof.
6, according to each described Industrial Boiler steam condenses system inhibiter of claim 1~3, it is characterized in that described polyoxyethylene sorbitan fatty acid ester is polyoxyethylene (18~a 20) anhydrous sorbitol monopalmitate, polyoxyethylene (18~22) sorbitan monostearate, polyoxyethylene (21~26) sorbitan monooleate or trioleate.
7, according to each described Industrial Boiler steam condenses system inhibiter of claim 1~3, it is characterized in that described sorbitan fatty acid ester is the anhydrous sorbitol monopalmitate, sorbitan monostearate or tristearate or sorbitan monooleate or trioleate.
8, the manufacture method according to each described Industrial Boiler steam condenses system inhibiter of claim 1~3 comprises the following steps:
1. in having the container of stirring, add suitable quantity of water, be warming up to 50 ℃~70 ℃, add the polyoxyethylene sorbitan fatty acid ester by described weight part, sorbitan fatty acid ester, the alkylamine of 12~18 carbon atoms or its epoxidized alkyl amine stir the homogeneous postcooling to room temperature;
2. add hexahydroaniline by described weight part in reactor, stir and add the material that morpholine and step obtain in 1. again, stirring must emulsion liquid product inhibiter after 2~15 minutes.
9, according to the purposes of each described Industrial Boiler steam condenses system inhibiter of claim 1~3 in various industrial steam boilers and condensate system.
CNB2004100031415A 2004-02-06 2004-02-06 Corrosion inhibitor for steam condensate system of industrial boiler and process for manufacturing same Expired - Fee Related CN1304306C (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103710711A (en) * 2014-01-07 2014-04-09 北京化工大学 Octadecylamine emulsion and preparation technology thereof
RU2515871C2 (en) * 2012-03-30 2014-05-20 Общество с ограниченной ответственностью "Научно-производственная фирма "ТРАВЕРС" (ООО "НПФ ТРАВЕРС") Inhibitor of carbonic acid corrosion for steam-generating installations of low and medium pressure aminat pk-1
CN104025200A (en) * 2012-02-28 2014-09-03 阿海珐有限公司 Method for purifying and conditioning the water-steam circuit of a power plant, especially of a nuclear power plant
RU2613356C1 (en) * 2015-12-18 2017-03-16 Общество с ограниченной ответственностью "Тепло-ЭнергоСервис" Method of feed water preparation for low pressure coil steam generators
CN110330122A (en) * 2019-05-30 2019-10-15 广东智淳环境科技有限公司 A kind of multi-functional environment-protection water treatment agent and preparation method thereof
CN110342654A (en) * 2019-05-30 2019-10-18 广东智淳环境科技有限公司 A kind of novel non-phosphate corrosion inhibiting and descaling agent and preparation method thereof
CN111334802A (en) * 2020-04-09 2020-06-26 苏州热工研究院有限公司 Film-forming amine corrosion inhibitor suitable for nuclear power plant secondary circuit shutdown maintenance and method for reducing secondary circuit corrosion during nuclear power plant shutdown

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US4681737A (en) * 1985-09-17 1987-07-21 Calgon Corporation Stabilized sodium erythorbate boiler corrosion inhibitor compositions and methods
JP2812623B2 (en) * 1992-09-11 1998-10-22 オルガノ株式会社 Boiler water treatment method
CN1115306C (en) * 1998-12-23 2003-07-23 王福霖 Corrosion-retarding scale inhibitor for boiler
JP2002294273A (en) * 2001-03-30 2002-10-09 Hakuto Co Ltd Water corrosion preventing agent composition
JP2003120904A (en) * 2001-08-09 2003-04-23 Miura Co Ltd Water treating agent for steam boiler device

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104025200A (en) * 2012-02-28 2014-09-03 阿海珐有限公司 Method for purifying and conditioning the water-steam circuit of a power plant, especially of a nuclear power plant
US9943890B2 (en) 2012-02-28 2018-04-17 Areva Gmbh Method for cleaning and conditioning the water-steam circuit of a power plant, especially of a nuclear power plant
RU2515871C2 (en) * 2012-03-30 2014-05-20 Общество с ограниченной ответственностью "Научно-производственная фирма "ТРАВЕРС" (ООО "НПФ ТРАВЕРС") Inhibitor of carbonic acid corrosion for steam-generating installations of low and medium pressure aminat pk-1
CN103710711A (en) * 2014-01-07 2014-04-09 北京化工大学 Octadecylamine emulsion and preparation technology thereof
RU2613356C1 (en) * 2015-12-18 2017-03-16 Общество с ограниченной ответственностью "Тепло-ЭнергоСервис" Method of feed water preparation for low pressure coil steam generators
CN110330122A (en) * 2019-05-30 2019-10-15 广东智淳环境科技有限公司 A kind of multi-functional environment-protection water treatment agent and preparation method thereof
CN110342654A (en) * 2019-05-30 2019-10-18 广东智淳环境科技有限公司 A kind of novel non-phosphate corrosion inhibiting and descaling agent and preparation method thereof
CN110330122B (en) * 2019-05-30 2021-12-21 智淳新材料科技(广州)有限公司 Multifunctional environment-friendly water treatment agent and preparation method thereof
CN111334802A (en) * 2020-04-09 2020-06-26 苏州热工研究院有限公司 Film-forming amine corrosion inhibitor suitable for nuclear power plant secondary circuit shutdown maintenance and method for reducing secondary circuit corrosion during nuclear power plant shutdown
CN111334802B (en) * 2020-04-09 2022-05-24 苏州热工研究院有限公司 Film-forming amine corrosion inhibitor suitable for nuclear power plant secondary circuit shutdown maintenance and method for reducing secondary circuit corrosion during nuclear power plant shutdown

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