US3378581A - Diamine salts useful for inhibiting the corrosion in return steam condensate lines - Google Patents
Diamine salts useful for inhibiting the corrosion in return steam condensate lines Download PDFInfo
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- US3378581A US3378581A US127821A US12782161A US3378581A US 3378581 A US3378581 A US 3378581A US 127821 A US127821 A US 127821A US 12782161 A US12782161 A US 12782161A US 3378581 A US3378581 A US 3378581A
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- corrosion
- steam
- condensate
- inhibiting
- boiler
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- 230000007797 corrosion Effects 0.000 title description 25
- 238000005260 corrosion Methods 0.000 title description 25
- -1 Diamine salts Chemical class 0.000 title description 11
- 230000002401 inhibitory effect Effects 0.000 title description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 150000004985 diamines Chemical class 0.000 claims description 7
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 description 22
- 238000012360 testing method Methods 0.000 description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000000126 substance Substances 0.000 description 10
- 125000005263 alkylenediamine group Chemical group 0.000 description 8
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000003760 tallow Substances 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical class CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 229910001369 Brass Inorganic materials 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- KYARBIJYVGJZLB-UHFFFAOYSA-N 7-amino-4-hydroxy-2-naphthalenesulfonic acid Chemical compound OC1=CC(S(O)(=O)=O)=CC2=CC(N)=CC=C21 KYARBIJYVGJZLB-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 241001306288 Ophrys fuciflora Species 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 150000001243 acetic acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001279 adipic acids Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 150000002311 glutaric acids Chemical class 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 150000002691 malonic acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 210000002445 nipple Anatomy 0.000 description 1
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 1
- GJNDMSSZEBNLPU-UHFFFAOYSA-N octadecylurea Chemical compound CCCCCCCCCCCCCCCCCCNC(N)=O GJNDMSSZEBNLPU-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 150000002913 oxalic acids Chemical class 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000003047 pimelic acids Chemical class 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003330 sebacic acids Chemical class 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003442 suberic acids Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003444 succinic acids Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
Classifications
-
- 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
- C23F11/10—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 using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/141—Amines; Quaternary ammonium compounds
- C23F11/143—Salts of amines
Definitions
- This invention relates to novel compounds which are useful in inhibiting corrosion in return steam condensate lines. More particularly, the subject invention is directed to new compositions of matter which are organic acid salts of the reaction product of an alkylene oxide and a substituted alkylene diamine.
- the principal object of the present invention is to provide compositions of matter for the treatment of steam condensates which produce improved results in preventing or minimizing corrosion in steam lines, traps, condensers, valves, and in other parts of steam systems such as turbine blades.
- the corrosion in steam and condensate return systems may be prevented or substantially mitigated by treating such systems with a corrosion inhibiting amount of a carboxylic acid salt of the reaction product of a low molecular weight alkylene oxide and a substituted alkylene diamine.
- a corrosion inhibiting amount of a carboxylic acid salt of the reaction product of a low molecular weight alkylene oxide and a substituted alkylene diamine are effective when added either to the boiler feedwater, to the steam lines, or to the condensate return lines.
- a slightly excessive amount to insure that enough of the chemical steam distills into the steam and condensate return systems.
- it is preferred to add the treatment to the steam condensate line since it is this part of the system where corrosive attack is the severest and the smallest amounts of the treatment are the most effective. From a practical standpoint, the chemical is most conveniently applied to the boiler feedwater.
- the amount of treatment should be at least 1 part per million of the corrosion inhibiting chemical by weight of the steam or steam condensate, preferably 2 to 5 parts per million and even more preferably 10 to 25 parts per million.
- the dosage will, of course, vary depending on the conditions of the system and other variable factors and hence, dosages as high as to parts per million may be necessary under extraordinarily corrosive conditions.
- the employment of the corrosion inhibiting chemicals in accordance with this invention is applicable to the generation of steam at various temperatures and pressures. Good results can be obtained where steam is generated under atmospheric conditions, subatmospheric conditions or superatmospheric conditions. In most cases, steam is generated at pressures from atmospheric up to 1500 pounds per square inch or more and the corresponding temperatures.
- substituted alkylene diamines which are used as starting materials in preparing the compositions useful in the practice of the invention have the following general formula:
- R is an acyclic hydrocarbon radical containing from 10 to 32 carbon atoms and n is an integer from 2 to 6.
- the radical R is conveniently derived from a saturated or unsaturated fatty group.
- Such groups as dodecyl, tetradecyl, hexadecyl, octadecyl, octadecenyl, and octadecadienyl may be substituents with good results being obtained in each instance. Extremely good results are afforded when R is a mixture of alkyl radicals such as are found in vegetable oils and animal fats. Coco, soya and tallow are examples of such mixed natural radicals.
- the diarnine portion of the compounds described above may be one of any number of the known diamines.
- Ethylene diarnine, 1,2 propylene diamine, 1,3 propylene diamine and hexamethylene diamine are several examples.
- the substituted alkylene diamines may be prepared by several difierent techniques.
- the alkylene diamines may be alkylated with an alkyl halide to produce the desired product.
- Such a method is illustrated in Kyrides US. Patent 2,246,524.
- Another method is to react an alkylamine with acrylonitrile and then hydrogenate whereby an alkyl substituted propylene diamine is produced.
- Commerically available N-alkyl propylene diamines are the products manufactured by the Armour Chemical Division under the trade name, Duomeens.
- Duomeens are N-lauryl propylene diamine; N- coco propylene diamine; N-soya'propylene diamine, and N-tallow propylene diamine.
- the substituted alkylene diamines thus described are capable of being reacted with varying amounts of several of the well known low molecular weight alkylene oxides, such as ethylene oxide, 1,2-propylene oxide, butylene oxide or the like, to produce products varying in their physical and chemical properties.
- the hydroxyalkylated, substituted alkylene diamines must be water dispersible to the extent that 5% by weight or more forms a uniform dispersion in aqueous media. This is usually accomplished by hydroxyalkylating 1 mol of diamine with 1 to 4, and preferably 2-3, mols of ethylene oxide or other alkylene oxide to produce the degree of water dispersibility desired.
- the hydroxyalkylation of the products may be performed by any one of several well known methods. Since there are three reactive hydrogen atoms in the alkyl substituted diamines the hydroxyalkylation could conceiva'bly take place at any of the sites. Hence, one mol of an alkylene oxide could react with any one of the three hydrogen atoms to produce a mixture of hydroxyalkylated products. Several of these reaction products are The salt forming aliphatic carboxylic acids should not exceed carbon atoms in chain length. For purpose of classification the acids may be divided into four classes:
- class I such acids as acetic, propionic, n-butyric, isobutyric, n-heptylic, caprylic and prelargonic acids may be used.
- class II are oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic and sebacic acids.
- Glycolic, gluconic, glyceric and lactic acids are illustrative of class III.
- Class IV would include such acids as malic and citric.
- the salts listed in Table II were prepared by heating the compositions in Table I, which ranged from viscous liquids to pastes, and adding the acid, with continued heat, until a homogeneous product was produced.
- compositions of the invention When boiler feedwater applications are contemplated it is sometimes helpful to formulate the compositions of the invention with boiler antifoams.
- the compositions of the invention will not produce foaming or priming when used at the concentrations recommended herein, but in the event high concentrations occur in the boiler water, the use of antifoams is a safeguard to insure good operation of the boiler.
- Antifoams that may be used are those described in US. Patents 2,575,298, 2,626,243, 2,575,276, 2,609,344 and 2,717,881. Only a few parts per million of these antifoams in the boiler water are required to insure against any harmful foaming.
- compositions of the invention provided superior corrosion protection as against the poor or slight protection afforded by other inhibitors tested.
- the corrosion test specimens consisted of 1 inch x 2 inch panels which were sheared from a single sheet of 22 gauge cold rolled mild steel. All specimens were uniformly sandblasted before being immersed in the bath.
- Example I In this series the two compositions, composition VIII, Table II and composition IX, Table II were each tested separately at 10 parts per million. At the end of the 6th day the weight losses were 221 and 121 milligrams, respectively.
- Example II This test was conducted in an actual boiler system to determine whether composition XVI would be detrimental to normal boiler operation.
- the test boiler generated a total of 800,000 to 1,000,000 pounds of steam per day at 125 pounds per inch.
- Composition XVI was fed by dispersing 1 gallon into 30 to 40 gallons of condensate return and injecting it directly into the steam header. The dosage for the entire test period was maintained at parts per million of the steam.
- a by-pass corrosion test loop was installed in front of one of the condensatereturn pumps. This loop was approximately 3,000 feet from the boiler and 400 to 700 gallons passed through per day. The specimen was a 1 inch pipe nipple which was placed in the system with appropriate fittings.
- water dispersible as used herein means a material which in water or other aqueous media does not form a true solution yet it is capable of remaining in a suspended condition at the concentrations herein specified for relatively long periods of time. These suspensions may or may not be colloidal.
- citric acid salt of the reaction product of ethylene oxide and N-tallow propylene diamine in a mol ratio of about 3 mols of ethylene oxide per mol of said diamine.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
United States Patent 4 Claims. c1. 266-50117) The subject application is a divisional application of my copending application Ser. No. 583,397 which was filed on May 10, 1956.
This invention relates to novel compounds which are useful in inhibiting corrosion in return steam condensate lines. More particularly, the subject invention is directed to new compositions of matter which are organic acid salts of the reaction product of an alkylene oxide and a substituted alkylene diamine.
It is well known that steam lines and steam condensate lines are subject to corrosion which is very difficult to control. This corrosion is apparently due, to a large extent, to carbon dioxide and oxygen in the boiler-steamcondeusate system. Carryover from the boiler water can also increase the corrosion. The problem of corrosion of the internal surfaces of steam condensate return lines has been recognized for many years. Generally, the difficulties that have been experienced are pitting, grooving and ultimate deterioration of sections of the condensate return system and the plugging of constrictions in the system with the insoluble products of corrosion. To evaluate properly the actual cost of return line corrosion, it is necessary not only to consider the loss in terms of labor, curtailed production and the cost of the material destroyed, but also to weigh effects in terms of inelficient operation of fouled equipment.
Experimental studies by various investigators indicate that dissolved carbon dioxide and oxygen are responsible for practically all the corrosion in the condensate lines. The various expedients that have been devised for combating this attack are as follows:
(1) The use of corrosion resistant alloys, which is generally prohibitive from a cost standpoint.
(2) Minimizing the amount of carbon dioxide and oxygen in the condensate either by venting or pretreatment of the boiler feedwater.
(3) Chemical treatment of the condensate.
It is known to use a readily volatile alkaline amine material for protection against corrosion in steam and return condensate lines but the results obtained with such amines have sometimes left much to be desired, particularly in steam and condensate systems of great length or in tall buildings. Moreover, these amines to be effective, are usually required in amounts which are roughly pro- \portional to the carbon dioxide content of the condensate. Where the return of condensate to the boiler constitutes a minor fraction of the boiler feed, such treatment often becomes economically impractical.
Where high pressure steam is required to operate industrial devices, such as turbines, it has been the experience of the art that certain treating agents will undergo decomposition and form deposits on the surfaces of the devices which, in many instances, will necessitate costly shutdowns and repairs.
It would be desirable to have a chemical treatment capable of being applied to any part of a steam or condensate return system at small, economical dosages and have beneficial results obtained in all cases.
The principal object of the present invention is to provide compositions of matter for the treatment of steam condensates which produce improved results in preventing or minimizing corrosion in steam lines, traps, condensers, valves, and in other parts of steam systems such as turbine blades.
It has been found that the corrosion in steam and condensate return systems may be prevented or substantially mitigated by treating such systems with a corrosion inhibiting amount of a carboxylic acid salt of the reaction product of a low molecular weight alkylene oxide and a substituted alkylene diamine. These materials are effective when added either to the boiler feedwater, to the steam lines, or to the condensate return lines. When added to the boiler feedwater it is generally necessary to add a slightly excessive amount to insure that enough of the chemical steam distills into the steam and condensate return systems. Generally, however, it is preferred to add the treatment to the steam condensate line since it is this part of the system where corrosive attack is the severest and the smallest amounts of the treatment are the most effective. From a practical standpoint, the chemical is most conveniently applied to the boiler feedwater.
The amount of treatment should be at least 1 part per million of the corrosion inhibiting chemical by weight of the steam or steam condensate, preferably 2 to 5 parts per million and even more preferably 10 to 25 parts per million. The dosage will, of course, vary depending on the conditions of the system and other variable factors and hence, dosages as high as to parts per million may be necessary under extraordinarily corrosive conditions.
The employment of the corrosion inhibiting chemicals in accordance with this invention is applicable to the generation of steam at various temperatures and pressures. Good results can be obtained where steam is generated under atmospheric conditions, subatmospheric conditions or superatmospheric conditions. In most cases, steam is generated at pressures from atmospheric up to 1500 pounds per square inch or more and the corresponding temperatures.
The substituted alkylene diamines which are used as starting materials in preparing the compositions useful in the practice of the invention have the following general formula:
wherein R is an acyclic hydrocarbon radical containing from 10 to 32 carbon atoms and n is an integer from 2 to 6.
The radical R is conveniently derived from a saturated or unsaturated fatty group. Such groups as dodecyl, tetradecyl, hexadecyl, octadecyl, octadecenyl, and octadecadienyl may be substituents with good results being obtained in each instance. Extremely good results are afforded when R is a mixture of alkyl radicals such as are found in vegetable oils and animal fats. Coco, soya and tallow are examples of such mixed natural radicals.
The diarnine portion of the compounds described above may be one of any number of the known diamines. Ethylene diarnine, 1,2 propylene diamine, 1,3 propylene diamine and hexamethylene diamine are several examples.
The substituted alkylene diamines may be prepared by several difierent techniques. For instance, the alkylene diamines may be alkylated with an alkyl halide to produce the desired product. Such a method is illustrated in Kyrides US. Patent 2,246,524. Another method is to react an alkylamine with acrylonitrile and then hydrogenate whereby an alkyl substituted propylene diamine is produced. Commerically available N-alkyl propylene diamines are the products manufactured by the Armour Chemical Division under the trade name, Duomeens.
Specific Duomeens are N-lauryl propylene diamine; N- coco propylene diamine; N-soya'propylene diamine, and N-tallow propylene diamine.
The substituted alkylene diamines thus described are capable of being reacted with varying amounts of several of the well known low molecular weight alkylene oxides, such as ethylene oxide, 1,2-propylene oxide, butylene oxide or the like, to produce products varying in their physical and chemical properties. To be suitable for present purposes, the hydroxyalkylated, substituted alkylene diamines must be water dispersible to the extent that 5% by weight or more forms a uniform dispersion in aqueous media. This is usually accomplished by hydroxyalkylating 1 mol of diamine with 1 to 4, and preferably 2-3, mols of ethylene oxide or other alkylene oxide to produce the degree of water dispersibility desired.
The hydroxyalkylation of the products may be performed by any one of several well known methods. Since there are three reactive hydrogen atoms in the alkyl substituted diamines the hydroxyalkylation could conceiva'bly take place at any of the sites. Hence, one mol of an alkylene oxide could react with any one of the three hydrogen atoms to produce a mixture of hydroxyalkylated products. Several of these reaction products are The salt forming aliphatic carboxylic acids should not exceed carbon atoms in chain length. For purpose of classification the acids may be divided into four classes:
(I) Aliphatic monocarboxylic acids (II) Aliphatic dicarboxylic acids (III) Hydroxy substituted carboxylic acids (IV) Hydroxy substituted polycarboxylic acids In class I such acids as acetic, propionic, n-butyric, isobutyric, n-heptylic, caprylic and prelargonic acids may be used. Examples of class II are oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic and sebacic acids. Glycolic, gluconic, glyceric and lactic acids are illustrative of class III. Class IV would include such acids as malic and citric.
For purposes of illustration, several aliphatic carboxylic acid salts of the alkyl substituted propylene di-amines listed in Table I are shown below in Table II.
TABLE II Composition Composition Aliphatic Mol Ratio Number Number Oarboxylic Reaction Table I Acid ProductzAcid I Acetic acid 1:1
I Lactic acid 1:1
I Citric acid 1:1
III Butyric acid 1:1
IV Malic acid... 1:1
V Succim'c acid 1:1
I Malonic acid 2:1
I Adipic acid. 1:1
The salts listed in Table II were prepared by heating the compositions in Table I, which ranged from viscous liquids to pastes, and adding the acid, with continued heat, until a homogeneous product was produced.
When boiler feedwater applications are contemplated it is sometimes helpful to formulate the compositions of the invention with boiler antifoams. The compositions of the invention will not produce foaming or priming when used at the concentrations recommended herein, but in the event high concentrations occur in the boiler water, the use of antifoams is a safeguard to insure good operation of the boiler. Antifoams that may be used are those described in US. Patents 2,575,298, 2,626,243, 2,575,276, 2,609,344 and 2,717,881. Only a few parts per million of these antifoams in the boiler water are required to insure against any harmful foaming.
EVALUATION OF THE INVENTION (A) Screening tests.The material to be tested was added, at a concentration of parts per million, to 350 ml. of deionized water contained in a 400 ml. beaker. The beaker was held in an oil bath at a temperature of about F. The solution was stirred at about 1750 rpm. with centrifugal-type glass stirrers. A mixture of CO and air was bubbled through the solution during the test. A mild steel specimen was sandblasted, weighed, and placed in the solution overnight. The weight loss of the specimen was then determined. A similar test, called the blank, was made under identical conditions except that no corrosion inhibitor was added to the water. The data from these screening tests are presented in Table III as percent protection compared with the blank test.
TABLE III Composition: Percent protection Composition IX, Table II 93 Sebacic acid 11 Sodium hexametaphosphate 19 Octadecyl urea 0 From the above it is evident the compositions of the invention provided superior corrosion protection as against the poor or slight protection afforded by other inhibitors tested.
(B) Experimental condensate corrosion tests.This series of corrosion tests were made in an apparatus designed to simulate a severely corrosive condition which might be encountered in a steam condensate system. In this apparatus a synthetic condensate was produced ina glass tower by aerating heated distilled water with a mixture of carbon dioxide and air. This condensate and a solution of the treating chemical were proportioned into a test container by gravity feed. A number of steel test coupons were suspended in the latter and the liquid was mildly agitated with a paddle stirrer. At periodic intervals a test specimen was removed from the bath and the weight loss determined. The temperature, free carbon dioxide and dissolved oxygen of the synthetic condensate, and the treatment concentration were controlled throughout the test.
The corrosion test specimens consisted of 1 inch x 2 inch panels which were sheared from a single sheet of 22 gauge cold rolled mild steel. All specimens were uniformly sandblasted before being immersed in the bath.
Agitation of the liquid was initiated and the water in the bath was heated to and thermostatically controlled at i1 F. The free carbon dioxide and dissolved oxygen of the water were maintained at 45 14 parts per million and 3.5 1 10.2 parts per million, respectively.
A complete, detailed description of the test apparatus and method is described in the article, A Laboratory Method for the Study of Steam Condensate Corrosion Inhibitors, by H. I. Patzelt, Corrosion, January 1953.
The following examples illustrate the results obtained in the evaluation of test specimens using treating chemicals within the scope of the invention.
Example I In this series the two compositions, composition VIII, Table II and composition IX, Table II were each tested separately at 10 parts per million. At the end of the 6th day the weight losses were 221 and 121 milligrams, respectively.
The corrosive conditions maintained in these tests when compared with most industrial condensate return systems are extremely severe. Inhibitors giving only good to fair results in the test in most cases give outstanding results in actual use at lower dosages.
(C) Effect'on brass.-The screening test method (A above) was used, Brass specimens in place of the steel were suspended in deionized water. Rather than running a percent comparison against the blank, weight losses in milligrams were determined. Composition XVI showed a weight loss of only 13.2 milligrams.
Example II This test was conducted in an actual boiler system to determine whether composition XVI would be detrimental to normal boiler operation. The test boiler generated a total of 800,000 to 1,000,000 pounds of steam per day at 125 pounds per inch. Composition XVI was fed by dispersing 1 gallon into 30 to 40 gallons of condensate return and injecting it directly into the steam header. The dosage for the entire test period was maintained at parts per million of the steam.
A by-pass corrosion test loop was installed in front of one of the condensatereturn pumps. This loop was approximately 3,000 feet from the boiler and 400 to 700 gallons passed through per day. The specimen was a 1 inch pipe nipple which was placed in the system with appropriate fittings.
The test was run for one month at the end of which time inspection revealed corrosion rates of the specimen were being satisfactorily controlled. A sample of condensate was collected from the by-pass loop and analysis showed it to contain 2.0:06 parts per million of composition XVI. Of interest is the fact that the sample thus taken was at a point most remote from the boiler. There was no evidence of deposits forming in the system and no unusual foaming occurred in the boiler.
The expression water dispersible as used herein means a material which in water or other aqueous media does not form a true solution yet it is capable of remaining in a suspended condition at the concentrations herein specified for relatively long periods of time. These suspensions may or may not be colloidal.
I claim:
1. Salts of an aliphatic carboxylic acid and salts of the reaction product of 3 mols of ethylene oxide per mol of a substituted alkylene diamine of the formula RNCH2CH2-CH2NH wherein R is a long chain acyclic hydrocarbon radical 5 containing 10 to 32 carbon atoms, the salt forming, aliphatic carboxylic acid being selected from the group consisting of acetic, propionic, n-butyric, isobutyric, nheptyl'ic, caprylic, pelargonic, oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, glycolic, gluconic, glyceric, lactic, malic and citric.
l0 2. The acetic acid salt of the reaction product of ethylene oxide and N-tallow propylene diamine in 9. mol ratio of about 3 mols'of ethylene oxide per mol of said diamine.
3. The lactic acid salt of the reaction product of ethylene oxide and N-tallow propylene diamine in a mol ratio of about 3 mols of ethylene oxide per mol of said diamine.
4. The citric acid salt of the reaction product of ethylene oxide and N-tallow propylene diamine in a mol ratio of about 3 mols of ethylene oxide per mol of said diamine.
References Cited UNITED STATES PATENTS 2,243,329 5/1941 De Groote 260583 2,701,239 2/1955 Ryznar 260584 2,739,980 3/1956 Chester 260501 2,759,021 8/1956 Gaar et a1 260584 2,920,040 1/1960 Jolly 260-501 n 2,552,531 5/1951 De Groote 260501 2,868,833 1/1959 Szabo et al. 260-501 2,914,557 11/1959 Oxford 260-501 2,995,603 8/1961 Hutchison 260--501 3,029,125 4/1962 Hummel 212.7
2,143,388 1/1939 Schlock 260501 2,736,658 2/1956 Pfohl et a1. 260501 2,952,707 9/1960 Nikawitz 260501 X 2,930,761 3/ 1960 Charret 260584 X 40 OTHER REFERENCES Industrial and Engineering Chemistry, vol. 41, No. 10, October 1949, pp. 20802090.
LEON ZITVER, Examiner.
LORRAINE A. WEINBERGER, Primary Examiner.
M. B. WEBSTER, B. EISEN, Assistant Examiners.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,378,581 April 16, 1968 Louis E. Hummel It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:
Column 3, line 46, "prelargonic" should read pelargonic Column 5, line 44, after "and" cancel "salts". Column 6, line 34, "Schlock" should read Schlack Signed and sealed this 25th day of November 1969.
(SEAL) Attest:
Edward M'Fletcher, Jr. WILLIAM E. SCHUYLER, JR.
Attesting Officer Commissioner of Patents
Claims (1)
1. SALTS OF AN ALIPHATIC CARBOXYLIC ACID AND SALTS O THE REACTION PRODUCT OF 3 MOLS OF ETHYLENE OXIDE PER MOL OF A SUBSTITUTED ALKYLENE DIAMINE OF THE FORMULA
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US127821A US3378581A (en) | 1956-05-10 | 1961-07-31 | Diamine salts useful for inhibiting the corrosion in return steam condensate lines |
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US58339756A | 1956-05-10 | 1956-05-10 | |
US127821A US3378581A (en) | 1956-05-10 | 1961-07-31 | Diamine salts useful for inhibiting the corrosion in return steam condensate lines |
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US3997469A (en) * | 1975-02-26 | 1976-12-14 | Nalco Chemical Company | Corrosion inhibition with oil soluble diamides |
US4657740A (en) * | 1984-11-21 | 1987-04-14 | Betz Laboratories, Inc. | Method of scavenging oxygen from aqueous mediums |
US4693866A (en) * | 1984-11-21 | 1987-09-15 | Betz Laboratories, Inc. | Method of scavenging oxygen from aqueous mediums |
US5510044A (en) * | 1994-05-26 | 1996-04-23 | The University Of British Columbia | Composition for froth flotation of mineral ores comprising amine and frother |
US20050156137A1 (en) * | 2001-12-12 | 2005-07-21 | Kornelis Overkempe | Nitrogen-containing compounds as corrosion inhibitors |
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US20130233543A1 (en) * | 2001-12-12 | 2013-09-12 | Akzo Nobel N.V. | Nitrogen-containing compounds as corrosion inhibitors |
US8833450B2 (en) * | 2001-12-12 | 2014-09-16 | Akzo Nobel N.V. | Nitrogen containing compounds as corrosion inhibitors |
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